Polymeric acid catalysts and uses thereof

ABSTRACT

Polymers useful as catalysts in non-enzymatic saccharification processes are provided. Provided are also methods for hydrolyzing cellulosic materials into monosaccharides and/or oligosaccharides using these polymeric acid catalysts.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No.13/406,517, filed on Feb. 27, 2012, which claims priority to U.S.Provisional Patent Application No. 61/447,311 filed Feb. 28, 2011, andU.S. Provisional Patent Application No. 61/522,351 filed Aug. 11, 2011,which are incorporated herein by reference in their entireties.

FIELD

The present disclosure relates generally to catalysts that may be usedin saccharification of biomass, and more specifically to polymeric acidcatalysts that may be used to hydrolyze cellulose and/or hemicellulose.

BACKGROUND

Saccharification of cellulosic materials, particularly biomass wasteproducts of agriculture, forestry and waste treatment are of greateconomic and environmental relevance. As part of biomass energyutilization, attempts have been made to obtain ethanol (bioethanol) byhydrolyzing cellulose or hemicellulose, which are major constituents ofplants. The hydrolysis products, which include sugars and simplecarbohydrates, may then be subjected to further biological and/orchemical conversion to produce fuels or other commodity chemicals. Forexample, ethanol is utilized as a fuel or mixed into a fuel such asgasoline. Major constituents of plants include, for example, cellulose(a polymer glucose, which is a six-carbon sugar), hemicellulose (abranched polymer of five- and six-carbon sugars), lignin, and starch.Current methods for liberating sugars from lignocellulosic materials,however, are inefficient on a commercial scale based on yields, as wellas the water and energy used.

Work from the 1980's on the hydrolysis of β-glycosidic bonds usingperfluoronated solid superacid microporous resins, such as DupontNafion®, attempted to develop catalytic methods for use in digestingcellulose. Batch reactors and continuous-flow fixed-bed tube reactorswere used to demonstrate hydrolysis of cello-oligosaccharides tomonomeric sugars; however, these processes were unable to achieveappreciable digestion of cellulose or hemicellulose, and in particular,the crystalline domains of cellulose.

As such, there is an ongoing need for new catalysts that can efficientlygenerate sugar and sugar-containing products from biomass on acommercially-viable scale.

BRIEF SUMMARY

The present disclosure addresses this need by providing polymericmaterials that can be used to digest the hemicellulose and cellulose,including the crystalline domains of cellulose, in biomass.Specifically, the polymeric materials can hydrolyze the cellulose and/orhemicellulose into monosaccharides and/or oligosaccharides.

In one aspect, provided is a polymer having acidic monomers and ionicmonomers that are connected to form a polymeric backbone, in which eachacidic monomer has at least one Bronsted-Lowry acid, and each ionicmonomer independently has at least one nitrogen-containing cationicgroup or phosphorous-containing cationic group. In some embodiments,each acidic monomer has one Bronsted-Lowry acid. In other embodiments,some of the acidic monomers have one Bronsted-Lowry acid, while othershave two Bronsted-Lowry acids. In some embodiments, each ionic monomerhas one nitrogen-containing cationic group or phosphorous-containingcationic group. In other embodiments, some of the ionic monomers haveone nitrogen-containing cationic group or phosphorous-containingcationic group, while others have two nitrogen-containing cationicgroups or phosphorous-containing cationic groups.

In some embodiments, the Bronsted-Lowry acid at each occurrence isindependently selected from sulfonic acid, phosphonic acid, acetic acid,isophthalic acid, boronic acid, and perfluorinated acid. In certainembodiments, the Bronsted-Lowry acid at each occurrence is independentlysulfonic acid or phosphonic acid. In one embodiment, the Bronsted-Lowryacid at each occurrence is sulfonic acid.

In some embodiments, the one or more of the acidic monomers are directlyconnected to the polymeric backbone. In other embodiments, the one ormore of the acidic monomers each further include a linker connecting theBronsted-Lowry acid to the polymeric backbone. In certain embodiments,some of the Bronsted-Lowry acids are directly connected to the polymericbackbone, while other the Bronsted-Lowry acids are connected to thepolymeric backbone by a linker.

In those embodiments where the Bronsted-Lowry acid is connected to thepolymeric backbone by a linker, the linker at each occurrence isindependently selected from unsubstituted or substituted alkylene,unsubstituted or substituted cycloalkylene, unsubstituted or substitutedalkenylene, unsubstituted or substituted arylene, unsubstituted orsubstituted heteroarylene, unsubstituted or substituted alkylene ether,unsubstituted or substituted alkylene ester, and unsubstituted orsubstituted alkylene carbamate. In certain embodiments, the linker isunsubstituted or substituted arylene, unsubstituted or substitutedheteroarylene. In certain embodiments, the linker is unsubstituted orsubstituted arylene. In one embodiment, the linker is phenylene. Inanother embodiment, the linker is hydroxyl-substituted phenylene.

In those embodiments where the Bronsted-Lowry acid is connected to thepolymeric backbone by a linker, the Bronsted-Lowry acid and the linkerform a side chain. In some embodiments, each side chain mayindependently be selected from:

In some embodiments, the nitrogen-containing cationic group at eachoccurrence is independently selected from pyrrolium, imidazolium,pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium,pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, andpyrollizinium. In one embodiment, the nitrogen-containing cationic groupis imidazolium.

In some embodiments, the phosphorous-containing cationic group at eachoccurrence is independently selected from triphenyl phosphonium,trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium,tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.In one embodiment, the phosphorous-containing cationic group istriphenyl phosphonium.

In some embodiments, the one or more of the ionic monomers are directlyconnected to the polymeric backbone. In other embodiments, the one ormore of the ionic monomers each further include a linker connecting thenitrogen-containing cationic group or the phosphorous-containingcationic group to the polymeric backbone. In certain embodiments, someof the cationic groups are directly connected to the polymeric backbone,while other cationic groups are connected to the polymeric backbone by alinker.

In those embodiments where the nitrogen-containing cationic group islinked to the polymeric backbone by a linker, the nitrogen-containingcationic group and the linker form a side chain. In some embodiments,each side chain may independently be selected from:

In those embodiments where the phosphorous-containing cationic group islinked to the polymeric backbone by a linker, the phosphorous-containingcationic group and the linker form a side chain. In some embodiments,each side chain is independently selected from:

In those embodiments where the cationic group is connected to thepolymeric backbone by a linker, the linker at each occurrence isindependently selected from unsubstituted or substituted alkylene,unsubstituted or substituted cycloalkylene, unsubstituted or substitutedalkenylene, unsubstituted or substituted arylene, unsubstituted orsubstituted heteroarylene, unsubstituted or substituted alkylene ether,unsubstituted or substituted alkylene ester, and unsubstituted orsubstituted alkylene carbamate. In certain embodiments, the linker isunsubstituted or substituted arylene, unsubstituted or substitutedheteroarylene. In certain embodiments, the linker is unsubstituted orsubstituted arylene. In one embodiment, the linker is phenylene. Inanother embodiment, the linker is hydroxyl-substituted phenylene.

In some embodiments, the polymeric backbone is selected frompolyethylene, polypropylene, polyvinyl alcohol, polystyrene,polyurethane, polyvinyl chloride, polyphenol-aldehyde,polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam,and poly(acrylonitrile butadiene styrene).

In certain embodiments, the polymeric backbone is polyethylene orpolypropylene. In one embodiment, the polymeric backbone ispolyethylene. In another, the polymeric backbone is polyvinyl alcohol.In yet another embodiment, the polymeric backbone is polystyrene.

In other embodiments, the polymeric backbone is selected frompolyalkyleneammonium, polyalkylenediammonium, polyalkylenepyrrolium,polyalkyleneimidazolium, polyalkylenepyrazolium, polyalkyleneoxazolium,polyalkylenethiazolium, polyalkylenepyridinium,polyalkylenepyrimidinium, polyalkylenepyrazinium,polyalkylenepyradizimium, polyalkylenethiazinium,polyalkylenemorpholinium, polyalkylenepiperidinium,polyalkylenepiperizinium, polyalkylenepyrollizinium,polyalkylenetriphenylphosphonium, polyalkylenetrimethylphosphonium,polyalkylenetriethylphosphonium, polyalkylenetripropylphosphonium,polyalkylenetributylphosphonium, polyalkylenetrichlorophosphonium,polyalkylenetrifluorophosphonium, and polyalkylenediazolium.

In other embodiments, the polymeric backbone is alkyleneimidazolium,which refers to an alkylene moiety, in which one or more of themethylene units of the alkylene moiety has been replaced withimidazolium. In one embodiment, the polymeric backbone ispolyethyleneimidazolium, polyprolyeneimidazolium,polybutyleneimidazolium. It should further be understood that, in otherembodiments of the polymeric backbone, when a nitrogen-containingcationic group or a phosphorous-containing cationic group follows theterm “alkylene”, one or more of the methylene units of the alkylenemoiety is replaced with that particular nitrogen-containing cationicgroup or phosphorous-containing cationic group.

In some embodiments, the polymer is cross-linked. In certainembodiments, at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 99% ofthe polymer is cross-linked.

In some embodiments, the acidic monomers and the ionic monomers arerandomly arranged in an alternating sequence. In other embodiments, theacidic monomers and the ionic monomers are arranged in blocks ofmonomers. In certain embodiments where the acidic monomers and the ionicmonomers are arranged in blocks of monomers, each block has no more than20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, or 3monomers.

In some embodiments, the polymer further includes hydrophobic monomersconnected to the polymeric backbone, in which each hydrophobic monomerhas a hydrophobic group. In some embodiments, the hydrophobic group ateach occurrence is independently selected from an unsubstituted orsubstituted alkyl, an unsubstituted or substituted cycloalkyl, anunsubstituted or substituted aryl, or an unsubstituted or substitutedheteroaryl. In certain embodiments, the hydrophobic group at eachoccurrence is an unsubstituted or substituted aryl, or an unsubstitutedor substituted heteroaryl. In one embodiment, the hydrophobic group ateach occurrence is phenyl.

In some embodiments, the hydrophobic group is directly connected to thepolymeric backbone.

In some embodiments, the polymer further includes acidic-ionic monomersconnected to the polymeric backbone, in which each acidic-ionic monomerhas a Bronsted-Lowry acid and a cationic group. In some embodiments, thecationic group is a nitrogen-containing cationic group or aphosphorous-containing cationic group.

In certain embodiments, the Bronsted-Lowry acid at each occurrence inthe acidic-ionic monomer is independently selected from sulfonic acid,phosphonic acid, acetic acid, isophthalic acid, boronic acid, andperfluorinated acid. In certain embodiments, the Bronsted-Lowry acid ateach occurrence is independently sulfonic acid or phosphonic acid. Inone embodiment, the Bronsted-Lowry acid at each occurrence is sulfonicacid

In some embodiments, the nitrogen-containing cationic group at eachoccurrence in the acidic-ionic monomer is independently selected frompyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium,pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium,piperidinium, piperizinium, and pyrollizinium. In one embodiment, thenitrogen-containing cationic group is imidazolium.

In some embodiments, the phosphorous-containing cationic group at eachoccurrence in the acidic-ionic monomer is independently selected fromtriphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium,tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, andtrifluoro phosphonium. In one embodiment, the phosphorous-containingcationic group is triphenyl phosphonium.

In some embodiments, the one or more of the acidic-ionic monomers eachfurther includes a linker connecting the Bronsted-Lowry acid or thecationic group to the polymeric backbone. In those embodiments where theBronsted-Lowry acid or the cationic group is connected to the polymericbackbone by a linker in the acidic-ionic monomer, the linker at eachoccurrence is independently selected from unsubstituted or substitutedalkylene, unsubstituted or substituted cycloalkylene, unsubstituted orsubstituted alkenylene, unsubstituted or substituted arylene,unsubstituted or substituted heteroarylene, unsubstituted or substitutedalkylene ether, unsubstituted or substituted alkylene ester, andunsubstituted or substituted alkylene carbamate. In certain embodiments,the linker is unsubstituted or substituted arylene, unsubstituted orsubstituted heteroarylene. In certain embodiments, the linker isunsubstituted or substituted arylene. In one embodiment, the linker isphenylene. In another embodiment, the linker is hydroxyl-substitutedphenylene.

In those embodiments, where the Bronsted-Lowry acid and/or the cationicgroup of the acidic-ionic monomer is linked to the polymeric backbone bya linker, the Bronsted-Lowry acid and/or the cationic group and thelinker form a side chain of the acidic-ionic monomer. In someembodiments, each side chain of the acidic-ionic monomer mayindependently be selected from:

In some embodiments, the polymer has a total amount of Bronsted-Lowryacid of between 0.1 and 20 mmol, between 0.1 and 15 mmol, between 0.01and 12 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol, between 2and 7 mmol, between 3 and 6 mmol, between 1 and 5, or between 3 and 5mmol per gram of the polymer.

In some embodiments, at least a portion of the acidic monomers havesulfonic acid. In those embodiments where at least a portion of theacidic monomers have sulfonic acid, the total amount of sulfonic acid inthe polymer is between 0.05 and 10 mmol, between 1 and 8 mmol, orbetween 2 and 6 mmol per gram of polymer.

In some embodiments, at least a portion of the acidic monomers havephosphonic acid. In those embodiments where at least a portion of theacidic monomers have phosphonic acid in the polymer, the total amount ofphosphonic acid in the polymer is between 0.01 and 12 mmol, between 0.05and 10 mmol, between 1 and 8 mmol, or between 2 and 6 mmol per gram ofpolymer.

In some embodiments, at least a portion of the acidic monomers haveacetic acid. In those embodiments where at least a portion of the acidicmonomers have acetic acid, the total amount of acetic acid in thepolymer is between 0.01 and 12 mmol, between 0.05 and 10 mmol, between 1and 8 mmol, or between 2 and 6 mmol per gram of polymer.

In some embodiments, at least a portion of the acidic monomers haveisophthalic acid. In those embodiments where at least a portion of theacidic monomers have isophthalic acid, the total amount of isophthalicacid in the polymer is between 0.01 and 5 mmol, between 0.05 and 5 mmol,between 1 and 4 mmol, or between 2 and 3 mmol per gram of polymer.

In some embodiments, at least a portion of the acidic monomers haveboronic acid. In those embodiments where at least a portion of theacidic monomers have boronic acid, the total amount of boronic acid inthe polymer is between 0.01 and 20 mmol, between 0.05 and 10 mmol,between 1 and 8 mmol, or between 2 and 6 mmol per gram of polymer.

In some embodiments, at least a portion of the acidic monomers haveperfluorinated acid. In those embodiments where at least a portion ofthe acidic monomers have perfluorinated acid, the total amount ofperfluorinated acid in the polymer is between 0.01 and 5 mmol, between0.05 and 5 mmol, between 1 and 4 mmol, or between 2 and 3 mmol per gramof polymer.

In some embodiments, each ionic monomer further includes a counterionfor each nitrogen-containing cationic group or phosphorous-containingcationic group. In certain embodiments, the counterion at eachoccurrence is independently selected from halide, nitrate, sulfate,formate, acetate, or organosulfonate. In some embodiments, thecounterion is fluoride, chloride, bromide, or iodide. In one embodiment,the counterion is chloride. In another embodiment, the counterion issulfate. In yet another embodiment, the counterion is acetate.

In some embodiments, the polymer has a total amount ofnitrogen-containing cationic groups and counterions or a total amount ofphosphorous-containing cationic groups and counterions of between 0.01and 10 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol, between 2and 6 mmol, or between 3 and 5 mmol per gram of polymer.

In some embodiments, at least a portion of the ionic monomers haveimidazolium. In those embodiments where at least a portion of the ionicmonomers have imidazolium, the total amount of imidazolium andcounterions in the polymer is between 0.01 and 8 mmol, between 0.05 and8 mmol, between 1 and 6 mmol, or between 2 and 5 mmol per gram ofpolymer.

In some embodiments, at least a portion of the ionic monomers havepyridinium. In those embodiments where at least a portion of the ionicmonomers have pyridinium, the total amount of pyridinium and counterionsin the polymer is between 0.01 and 8 mmol, between 0.05 and 8 mmol,between 1 and 6 mmol, or between 2 and 5 mmol per gram of polymer.

In some embodiments, at least a portion of the ionic monomers havetriphenyl phosphonium. In those embodiments where at least a portion ofthe ionic monomers have triphenyl phosphonium, the total amount oftriphenyl phosphonium and counterions in the polymer is between 0.01 and5 mmol, between 0.05 and 5 mmol, between 1 and 4 mmol, or between 2 and3 mmol per gram of polymer.

Provided are also polymers selected from:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    nitrate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    nitrate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    iodide-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bromide-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    formate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-nitrate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bromide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-iodide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    formate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    acetate-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-4-boronyl-1-(4-vinylbenzyl)-pyridinium    chloride-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    nitrate-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene];-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    chloride-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenyl phosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium    chloride-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenyl phosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    bisulfate-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium    bisulfate-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    acetate-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenyl phosphonium    acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium    acetate-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenyl phosphonium    acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenylphosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenylphosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene)-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium nitrate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(butyl-vinylimidazolium chloride-co-butylimidazolium    bisulfate-co-4-vinylbenzenesulfonic acid);-   poly(butyl-vinylimidazolium bisulfate-co-butylimidazolium    bisulfate-co-4-vinylbenzenesulfonic acid);-   poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl    alcohol);-   poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzyl    alcohol).

In some embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene]; or-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene].

In other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene].-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene]; or-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    bisulfate-co-divinylbenzene].

In other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene].

In other embodiments, the polymer is:

-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene]; or-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene].

In other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridiniumchloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene]; or-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    chloride-co-divinylbenzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-co-divinyl benzene]; or-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    bisulfate-co-divinylbenzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-piperidine-co-divinyl benzene]; or-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    chloride-co-divinyl benzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    chloride-co-divinylbenzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene].

In yet other embodiments, the polymer is:

-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene].

In some embodiments, the polymer is:

-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    bisulfate-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene); or-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene).

In other embodiments, the polymer is:

-   poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl    alcohol).

In some embodiments, the polymer is:

-   poly(styrene-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene); or-   poly(styrene-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene).

In yet other embodiments, the polymer is:

-   poly(butyl-vinylimidazolium bisulfate-co-4-vinylbenzenesulfonic    acid-co-butylimidazolium bisulfate-co-styrene).

In some embodiments, the polymer described herein has one or morecatalytic properties selected from:

a) disruption of a hydrogen bond in cellulosic materials;

b) intercalation of the polymer into crystalline domains of cellulosicmaterials; and

c) cleavage of a glycosidic bond in cellulosic materials.

In some embodiments, the polymer has a greater specificity for cleavageof a glycosidic bond than dehydration of a monosaccharide in cellulosicmaterials.

In some embodiments, the polymer is capable of degrading biomass intoone or more sugars at a first-order rate constant of at least 0.001 perhour. In other embodiments, the polymer is capable of degrading biomassto produce the sugars at a first-order rate constant of at least 0.1, atleast 0.15, at least 0.2, at least 0.25, at least 0.3 or at least 0.5per hour.

In some embodiments, the polymer is capable of converting biomass intoone or more sugars and residual biomass, wherein the residual biomasshas a degree of polymerization of less than 300. In other embodiments,the polymer is capable of converting biomass into one or more sugars andresidual biomass, wherein the residual biomass has a degree ofpolymerization of less than 100, less than 90, less than 80, less than70, less than 60, or less than 50.

In some embodiments, the polymer is substantially insoluble in water oran organic solvent.

Provided is also a solid particle that includes a solid core and any ofthe polymers described herein, in which the polymer is coated on thesurface of the solid core. In some embodiments, the solid core is madeup of an inert material or a magnetic material. In one embodiment, thesolid core is made up of iron.

In some embodiments, the solid particle is substantially free of pores.

In other embodiments, the solid particle has catalytic activity. Incertain embodiments, at least about 50%, at least 60%, at least 70%, atleast 80%, at least 90% of the catalytic activity of the solid particleis present on or near the exterior surface of the solid particle.

Provided is also a composition that includes biomass and any of thepolymers described herein. In some embodiments, the composition furtherincludes a solvent. In one embodiment, the composition further includeswater. In some embodiments, the biomass has cellulose, hemicellulose, ora combination thereof. In yet other embodiments, the biomass also haslignin.

Provided is also a chemically-hydrolyzed biomass composition thatincludes any of the polymers described herein, one or more sugars, andresidual biomass. In some embodiments, the one or more sugars are one ormore monosaccharides, one or more oligosaccharides, or a mixturethereof. In other embodiments, the one or more sugars are two or moresugars that include at least one C4-C6 monosaccharide and at least oneoligosaccharide. In yet other embodiments, the one or more sugars areselected from glucose, galactose, fructose, xylose, and arabinose.

Provided is also a saccharification intermediate that includes any ofthe polymer described herein hydrogen-bonded to biomass. In certainembodiments of the saccharification intermediate, the ionic moiety ofthe polymer is hydrogen-bonded to the carbohydrate alcohol groupspresent in cellulose, hemicellulose, and other oxygen-containingcomponents of biomass. In certain embodiments of the saccharificationintermediate, the acidic moiety of the polymer is hydrogen-bonded to thecarbohydrate alcohol groups present in cellulose, hemicellulose, andother oxygen-containing components of lignocellulosic biomass, includingthe glycosidic linkages between sugar monomers. In some embodiments, thebiomass has cellulose, hemicellulose or a combination thereof.

Provided is also a method for degrading biomass into one or more sugars,by: a) providing biomass; b) contacting the biomass with any of thepolymers described herein and a solvent for a period of time sufficientto produce a degraded mixture, in which the degraded mixture has aliquid phase and a solid phase, and the liquid phase includes one ormore sugars, and the solid phase includes residual biomass; c) isolatingat least a portion of the liquid phase from the solid phase; and d)recovering the one or more sugars from the isolated liquid phase.

In some embodiments, the isolating of at least a portion of the liquidphase from the solid phase produces a residual biomass mixture, and themethod further includes: i) providing a second biomass; ii) contactingthe second biomass with the residual biomass mixture for a period oftime sufficient to produce a second degraded mixture, in which thesecond degraded mixture has a second liquid phase and a second solidphase, and the second liquid phase includes one or more second sugars,and wherein the second solid phase includes second residual biomass;iii) isolating at least a portion of the second liquid phase from thesecond solid phase; and iv) recovering the one or more second sugarsfrom the isolated second liquid phase.

In some embodiments, the method further includes contacting the secondbiomass and the residual biomass mixture with a second polymer, in whichthe second polymer can be any of the polymers described herein. In otherembodiments, the method further includes contacting the second biomassand the residual biomass mixture with a second solvent. In someembodiments, the method further includes recovering the polymer afterisolating at least a portion of the second liquid phase. In certainembodiments of the method, the solvent includes water.

In some embodiments of the method, the biomass has cellulose andhemicellulose, and the biomass is contacted with the polymer and thesolvent at a temperature and/or at a pressure suitable to preferentiallyhydrolyze the cellulose or suitable to preferentially hydrolyze thehemicellulose.

In some embodiments of the method, the one or more sugars are selectedfrom one or more monosaccharides, one or more oligosaccharides, or acombination thereof. In certain embodiments, the one or moremonosaccharides are one or more C4-C6 monosaccharides. In certainembodiments, the one or more sugars are selected from glucose,galactose, fructose, xylose, and arabinose.

In some embodiments, the method further includes pretreating the biomassbefore contacting the biomass with the polymer. In certain embodiments,the pretreatment of the biomass is selected from washing,solvent-extraction, solvent-swelling, comminution, milling, steampretreatment, explosive steam pretreatment, dilute acid pretreatment,hot water pretreatment, alkaline pretreatment, lime pretreatment, wetoxidation, wet explosion, ammonia fiber explosion, organosolventpretreatment, biological pretreatment, ammonia percolation, ultrasound,electroporation, microwave, supercritical CO₂, supercritical H₂O, ozone,and gamma irradiation, or a combination thereof.

In some embodiments of the method, the residual biomass has a degree ofpolymerization of less than 300. In other embodiments of the methods,the residual biomass has a degree of polymerization of less than 100,less than 90, less than 80, less than 70, less than 60, or less than 50.

In some embodiments of the method, the degrading of the biomass toproduce the sugars occurs at a first-order rate constant of at least0.001 per hour. In other embodiments of the method, the degrading of thebiomass to produce the sugars occurs at a first-order rate constant ofat least 0.1, at least 0.15, at least 0.2, at least 0.25, at least 0.3or at least 0.5 per hour.

Provided is also a method for pretreating biomass before hydrolysis ofthe biomass to produce one or more sugars, by: a) providing biomass; b)contacting the biomass with any of the polymers described herein and asolvent for a period of time sufficient to partially degrade thebiomass; and c) pretreating the partially degraded biomass beforehydrolysis to produce one or more sugars. In some embodiments, thebiomass has cellulose, hemicellulose, or a combination thereof. In otherembodiments, the biomass also has lignin. In some embodiments, thepretreatment of the partially degraded biomass mixture is selected fromwashing, solvent-extraction, solvent-swelling, comminution, milling,steam pretreatment, explosive steam pretreatment, dilute acidpretreatment, hot water pretreatment, alkaline pretreatment, limepretreatment, wet oxidation, wet explosion, ammonia fiber explosion,organosolvent pretreatment, biological pretreatment, ammoniapercolation, ultrasound, electroporation, microwave, supercritical CO₂,supercritical H₂O, ozone, and gamma irradiation, or a combinationthereof.

Provided is also a method of hydrolyzing pretreated biomass to produceone or more sugars, by: a) providing biomass pretreated according any ofthe pretreatment methods described herein; and b) hydrolyzing thepretreated biomass to produce one or more sugars. In some embodiments,the pretreated biomass is chemically hydrolyzed or enzymaticallyhydrolyzed. In some embodiments, the one or more sugars are selectedfrom the group consisting of glucose, galactose, fructose, xylose, andarabinose.

Provided is also a use of any of the polymers described herein fordegrading biomass into one or more monosaccharides, one or moreoligosaccharides, or a combination thereof. In some embodiments, the oneor more monosaccharides are one or more C4-C6 monosaccharides. In otherembodiments, the one or more sugars are selected from glucose,galactose, fructose, xylose, and arabinose. In some embodiments, thebiomass has cellulose, hemicellulose, or a combination thereof. In yetother embodiments, the biomass also has lignin.

Provided is also a use of any of the polymers described herein forpretreating biomass before further treatment using one or more methodsselected from washing, solvent-extraction, solvent-swelling,comminution, milling, steam pretreatment, explosive steam pretreatment,dilute acid pretreatment, hot water pretreatment, alkaline pretreatment,lime pretreatment, wet oxidation, wet explosion, ammonia fiberexplosion, organosolvent pretreatment, biological pretreatment, ammoniapercolation, ultrasound, electroporation, microwave, supercritical CO₂,supercritical H₂O, ozone, and gamma irradiation.

Provided is also a sugar composition obtained by any of the methods fordegrading biomass into one or more sugars described herein that employsany of the polymers described herein.

Provided is also a sugar composition obtained by contacting biomass withany of the polymers described herein for a period of time sufficient tohydrolyze the biomass into one or more sugars. In some embodiments, thesugar composition has at least 0.1%, at least 0.2%, at least 0.3%, atleast 0.4%, at least 0.5%, at least 0.6%, at least 0.7%, at least 0.8%or at least 0.9% by weight a mixture of sugars, wherein the mixture ofsugars comprises one or more C4-C6 monosaccharides and one or moreoligosaccharides. In certain embodiments of the sugar composition, theone or more C4-C6 monosaccharides are selected from glucose, galactose,fructose, xylose, and arabinose.

Provided is also a biofuel composition derived from any of the sugarcompositions described herein. In certain embodiments, the biofuelcomposition includes butanol, ethanol, or a mixture thereof.

Provided is also a method of preparing any of the polymers describedherein, by: a) providing a starting polymer; b) reacting the startingpolymer with a nitrogen-containing or phosphorous-containing compound toproduce an ionic polymer; and c) reacting the ionic polymer with an acidto produce any of the polymers described herein. In some embodiments,the starting polymer is selected from polyethylene, polypropylene,polyvinyl alcohol, polycarbonate, polystyrene, polyurethane, or acombination thereof. In certain embodiments, the starting polymer is apolystyrene. In certain embodiments, the starting polymer ispoly(styrene-co-vinylbenzylhalide-co-divinylbenzene). In anotherembodiment, the starting polymer ispoly(styrene-co-vinylbenzylchloride-co-divinylbenzene).

In some embodiments of the method to prepare any of the polymersdescribed herein, the nitrogen-containing compound is selected from apyrrolium compound, an imidazolium compound, a pyrazolium compound, anoxazolium compound, a thiazolium compound, a pyridinium compound, apyrimidinium compound, a pyrazinium compound, a pyradizimium compound, athiazinium compound, a morpholinium compound, a piperidinium compound, apiperizinium compound, and a pyrollizinium compound. In certainembodiments, the nitrogen-containing compound is an imidazoliumcompound.

In some embodiments of the method to prepare any of the polymersdescribed herein, the acid is selected from sulfuric acid, phosphoricacid, hydrochloric acid, acetic acid and boronic acid. In oneembodiment, the acid is sulfuric acid.

Provided is also a method of preparing any of the polymers describedherein having a polystyrene backbone, by: a) providing a polystyrene; b)reacting the polystyrene with a nitrogen-containing compound to producean ionic polymer; and c) reacting the ionic polymer with an acid toproduce a polymer. In certain embodiments, the polystyrene ispoly(styrene-co-vinylbenzylhalide-co-divinylbenzene). In one embodiment,the polystyrene ispoly(styrene-co-vinylbenzylchloride-co-divinylbenzene).

In some embodiments of the method to prepare any of the polymersdescribed herein having a polystyrene backbone, the nitrogen-containingcompound is selected from a pyrrolium compound, an imidazolium compound,a pyrazolium compound, an oxazolium compound, a thiazolium compound, apyridinium compound, a pyrimidinium compound, a pyrazinium compound, apyradizimium compound, a thiazinium compound, a morpholinium compound, apiperidinium compound, a piperizinium compound, and a pyrolliziniumcompound. In certain embodiments, the nitrogen-containing compound is animidazolium compound.

In some embodiments of the method to prepare any of the polymersdescribed herein having a polystyrene backbone, the acid is selectedfrom sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid andboronic acid. In one embodiment, the acid is sulfuric acid.

Provided is also a polymer prepared according to any of the methodsdescribed above. In certain embodiments, the polymer has one or morecatalytic properties selected from:

a) disruption of a hydrogen bond in cellulosic materials;

b) intercalation of the polymer into crystalline domains of cellulosicmaterials; and

c) cleavage of a glycosidic bond in cellulosic materials.

Provided is also a use of a polymer prepared according to any of themethods described above for degrading biomass into one or moremonosaccharides, one or more oligosaccharides, or a combination thereof.

Provided is also a use a polymer prepared according to any of themethods described above for partially digesting biomass beforepretreatment using one or more methods selected from the groupconsisting of washing, solvent-extraction, solvent-swelling,comminution, milling, steam pretreatment, explosive steam pretreatment,dilute acid pretreatment, hot water pretreatment, alkaline pretreatment,lime pretreatment, wet oxidation, wet explosion, ammonia fiberexplosion, organosolvent pretreatment, biological pretreatment, ammoniapercolation, ultrasound, electroporation, microwave, supercritical CO₂,supercritical H₂O, ozone, and gamma irradiation.

Provided are also polymeric acid catalysts that are polymers having aplurality of monomers, in which at least one monomer has an acidicmoiety, and at least one monomer includes an ionic moiety (e.g., acovalently-attached cationic group that can be coordinated to anexchangeable counter-ion). An exemplary polymer is provided in Formula(I):

[A_(a)B]_(b)  (I)

in which A represents monomer that have an acidic moiety and Brepresents monomers that have an ionic moiety (e.g., a cationic moiety,a basic moiety or a salt). The acidic moiety includes a Bronsted-Lowryacid, and the ionic moiety includes a nitrogen-containing functionalgroup. Moreover, a and b are stoichiometric coefficients, such that aand b together make up a substantial portion of the co-monomer subunitsof the polymer. For example, a and b together make up at least about30%, at least about 40%, at least about 50%, at least about 60%, atleast about 70%, at least about 80%, at least about 90%, at least about95%, at least about 99% or substantially all of the co-monomer subunitsof the polymer.

In some embodiments, the polymer of Formula (I) is a polymer of Formula(Ia):

[A_(a)B_(b)C]_(c)  (Ia),

which includes monomers C that are covalently bound to and arecross-linked with other monomers in the polymer, and c is astochoimetric coefficient.

In other embodiments, the polymer of formula (I) is a polymer of Formula(Ib):

[A_(a)B_(b)D]_(d)  (Ib),

which includes monomers D that are covalently bound to other monomers inthe polymer, and d is a stochoimetric coefficient.

In other embodiments, the polymer of formula (I) is a polymer of Formula(Ic):

[A_(a)B_(b)C_(c)D]_(d)  (Ic).

In certain embodiments, monomers D are non-functionalized moieties, suchas hydrophobic moieties (e.g., phenyl).

Another exemplary polymer is provided in Formula (II):

in which each of L_(a′) and L_(b′) is independently for each occurrencea linker or absent; each A′ for each occurrence is an acidic moiety;each B′ for each occurrence is an ionic (e.g., cationic) moiety; each nis independently for each occurrence 0, 1, 2, 3, 4, 5, or 6; and a and bare stoichiometric coefficients together make up a substantial portionof the co-monomer subunits of the polymer. For example, a and b togethermake up at least about 30%, at least about 40%, at least about 50%, atleast about 60%, at least about 70%, at least about 80%, at least about90%, at least about 95%, at least about 99% or substantially all of themonomers of the polymer. Each of L_(a′) and L_(b′) can independentlyhave a plurality of A′ moieties and B′ moieties, respectively.

Another exemplary polymer is provided in Formula (III):

in which each Ar is independently for each occurrence an aryl orheteroaryl moiety; each A′ for each occurrence is an acidic moiety; eachB′ for each occurrence is an ionic moiety (e.g., a cationic moiety);each XL for each occurrence is a cross-linking moiety; and a, b, c, andd are stochoimetric coefficients, such that when taken together make upa substantial portion of the co-monomer subunits of the polymer. Forexample, a, b, c, and d together make up at least about 30%, at leastabout 40%, at least about 50%, at least about 60%, at least about 70%,at least about 80%, at least about 90%, at least about 95%, at leastabout 99% or substantially all of the co-monomer subunits of thepolymer. Each Ar can independently have a plurality of A′ moieties, B′moieties, and XL moieties, respectively.

Another exemplary polymer is provided in Formula (IV):

in which each of L_(ab) is independently for each occurrence a linker orabsent; each AB for each occurrence is a moiety that includes an acidicand an ionic moiety (e.g., a cationic moiety); each n is independentlyfor each occurrence 0, 1, 2, 3, 4, 5, or 6; and ab is a stoichiometriccoefficient, such that ab makes up a substantial portion of theco-monomer subunits of the polymer. For example, ab makes up at leastabout 30%, at least about 40%, at least about 50%, at least about 60%,at least about 70%, at least about 80%, at least about 90%, at leastabout 95%, at least about 99% or substantially all of the co-monomersubunits of the polymer. Each of L_(ab) can independently have aplurality of acidic moieties and ionic moieties (e.g., cationicmoieties), respectively.

Where polymers such as Formula (I), (Ia), (Ib), (Ic), (II), (III), or(IV) are depicted herein, the connectivity as shown above does notrequire a block polymer, but can also include other configurations ofthe A and B monomers, including random polymers. Moreover, the depictionof attachment of the monomers, such as that of A to B, does not limitthe nature of the attachment of the monomers, such as A to B by way of acarbon-carbon bond, but can also include other attachments such as acarbon-heteroatom bond.

In certain embodiments, the polymer of Formula (I), (Ia), (Ib), (Ic),(II), (III), or (IV) can catalyze the break-down of polysaccharides suchas cellulose, and hemicellulose, for example, through cleavage of theglycosidic bond between sugar moieties. In general, it is the acidicmoiety on the polymer of Formula (I), (Ia), (Ib), (Ic), (II), (III), or(IV) that catalyzes the cleavage of the glycosidic bonds. However,polymer of Formula (I), (Ia), (Ib), (Ic), (II), (III), or (IV) alsoincludes an ionic moiety (e.g., a cationic moiety), which is generallypresent as a nitrogen containing salt. This salt functionality of thepolymer of Formula (I), (Ia), (Ib), (Ic), (II), (III), or (IV) canpromote the break-down of the tertiary structure of the polysaccharidesdescribed herein, such as cellulosic materials. For example, the ionicmoiety can disrupt inter- and intra-molecular hydrogen bonding inpolysaccharide materials (e.g., disrupting the tertiary structure of thematerial), which can allow the acidic moiety of the polymer to accessmore readily the glycosidic bonds of the polysaccharides. Accordingly,the combination of the two functional moieties on a single polymer canprovide for a catalyst that is effective in the break-down ofpolysaccharides using relatively mild conditions as compared to thosemethods that employ a more corrosive acid, or methods that employ harshconditions such as high temperatures or pressure.

DESCRIPTION OF THE FIGURES

The following description sets forth exemplary compositions, methods,parameters and the like. It should be recognized, however, that suchdescription is not intended as a limitation on the scope of the presentdisclosure but is instead provided as a description of exemplaryembodiments.

FIG. 1 illustrates a portion of an exemplary polymer that has apolymeric backbone and side chains.

FIG. 2 illustrates a portion of an exemplary polymer, in which a sidechain with the acidic group is connected to the polymeric backbone by alinker and in which a side chain with the cationic group is connecteddirectly to the polymeric backbone.

FIG. 3A illustrates a portion of an exemplary polymer, in which themonomers are randomly arranged in an alternating sequence.

FIG. 3B illustrates a portion of an exemplary polymer, in which themonomers are arranged in blocks of monomers, and the block of acidicmonomers alternates with the block of ionic monomers.

FIGS. 4A and 4B illustrate a portion of exemplary polymers withcross-linking within a given polymeric chain.

FIGS. 5A, 5B, 5C and 5D illustrate a portion of exemplary polymers withcross-linking between two polymeric chains.

FIG. 6A illustrates a portion of an exemplary polymer with apolyethylene backbone.

FIG. 6B illustrates a portion of an exemplary polymer with apolyvinylalcohol backbone.

FIG. 6C illustrates a portion of an exemplary polymer with an ionomericbackbone.

FIG. 7A illustrates two side chains in an exemplary polymer, in whichthere are three carbon atoms between the side chain with theBronsted-Lowry acid and the side chain with the cationic group.

FIG. 7B illustrates two side chains in another exemplary polymer, inwhich there are zero carbons between the side chain with theBronsted-Lowry acid and the side chain with the cationic group.

FIG. 8 depicts an exemplary arrangement of the linear beta-(1-4)-glucanchains in crystalline cellulose.

FIG. 9 depicts interactions that may occur during saccharificationbetween an exemplary polymer and the carbohydrate alcohol groups presentin biomass containing crystalline cellulose.

DETAILED DESCRIPTION

The following description sets forth exemplary methods, parameters andthe like. It should be recognized, however, that such description is notintended as a limitation on the scope of the present disclosure but isinstead provided as a description of exemplary embodiments.

Described herein are polymers that can be used, in some embodiments, asan acid catalyst to hydrolyze cellulosic materials to producemonosaccharides, as well as oligosaccharides. Such polymers are hereinreferred to as “polymeric acid catalysts”. In particular, the polymericacid catalysts provided herein can disrupt the hydrogen bondsuperstructure typically found in natural cellulosic materials, allowingthe acidic pendant groups of the polymer to come into chemical contactwith the interior glycosidic bonds in the crystalline domains ofcellulose.

Unlike traditional catalysts known in the art used to hydrolyzecellulosic materials (e.g., enzymes, concentrated acids or diluteaqueous acids), the polymeric acid catalysts described herein provideeffective cellulose digestion, as well as ease of recycle and reuse. Theability to recycle and reuse the catalyst presents several advantages,including reducing the cost of converting lignocellulose intoindustrially important chemicals, such as sugars, oligosaccharides,organic acids, alcohols and aldehydes. Unlike enzymes and dilute aqueousacids, the polymeric catalysts described herein can penetrate deeplyinto the crystalline structure of cellulose, resulting in higher yieldsand faster kinetics for hydrolyzing cellulosic materials to producemonosaccharides and/or oligosaccharides. Unlike concentrated acids,which require costly, energy-intensive solvent extraction and/ordistillation processes to recover the acid catalyst followinglignocellulose digestion, the polymeric catalysts described herein areless corrosive, more easily handled, and can be easily recovered becausethey naturally phase separate from aqueous products. Further, the use ofthe polymeric acid catalysts provided herein does not requiresolubilization of the cellulosic material in a solvent such as moltenmetal halides, ionic liquids, or acid/organic solvent mixtures. Thus,provided herein are stable, recyclable, polymeric catalysts that canefficiently digest cellulosic materials on a commercially-viable scale.

DEFINITIONS

As used herein, “alkyl” includes saturated straight-chain orbranched-chain monovalent hydrocarbon radicals, and combinations ofthese, which contain only C and H when unsubstituted. Examples includemethyl, ethyl, propyl, butyl and pentyl. When an alkyl residue having aspecific number of carbons is named, all geometric isomers having thatnumber of carbons are intended to be encompassed and described; thus,for example, “butyl” is meant to include n-butyl, sec-butyl, iso-butyl,and tert-butyl; “propyl” includes n-propyl, and iso-propyl. The totalnumber of carbon atoms in each such group is sometimes described herein.For example, when the group can contain up to ten carbon atoms it can berepresented as 1-10C or as C1-C10 or C1-10. In some embodiments, alkylmay be substituted. Suitable alkyl substituents may include, forexample, hydroxy, amino, and halo.

As used herein, “alkylene” refers to the same residues as alkyl, buthaving bivalency. Examples of alkylene include methylene (—CH₂—),ethylene (—CH₂CH₂—), propylene (—CH₂CH₂CH₂—), butylene (—CH₂CH₂CH₂CH₂—).

As used herein, “alkylene carbamate” refers to an alkylene moiety, inwhich one or more of the methylene units of the alkylene moiety has beenreplaced with a carbamate moiety (—C(O)—O—NR— or —O—C(O)—NR—, where Rcan be, for example, alkyl or aryl). In some embodiments, alkylenecarbamate may be substituted. Suitable alkylene carbamate substituentsmay include, for example, hydroxyl, amino, and halo.

As used herein, “alkylene ester” refers to an alkylene moiety, in whichone or more of the methylene units of the alkylene moiety has beenreplaced with an ester moiety (—C(O)—O— or —O—C(O)—). In someembodiments, alkylene ester may be substituted, further bearing one ormore substituents. Suitable alkylene ester substituents may include, forexample, hydroxyl, amino, and halo.

As used herein, “alkylene ether” refers to an alkylene moiety, in whichone or more of the methylene units of the alkylene moiety has beenreplaced with an ether moiety (—C(O)—). In some embodiments, alkyleneether may be substituted, further bearing one or more substituents.Suitable alkylene ether substituents may include, for example, hydroxyl,amino, and halo.

As used herein, “alkenyl” refers to an unsaturated hydrocarbon grouphaving at least one site of olefinic unsaturation (i.e., having at leastone moiety of the formula C═C). Alkenyl contains only C and H whenunsubstituted. When an alkenyl residue having a specific number ofcarbons is named, all geometric isomers having that number of carbonsare intended to be encompassed and described; thus, for example,“butenyl” is meant to include n-butenyl, sec-butenyl, and iso-butenyl.Examples of alkenyl may include —CH═CH₂, —CH₂—CH═CH₂ and—CH₂—CH═CH—CH═CH₂. In some embodiments, alkenyl may be substituted.Suitable alkyenyl substituents may include, for example, hydroxy, amino,and halo.

As used herein, “alkenylene” refers to the same residues as alkenyl, buthaving bivalency. Examples of alkenylene include ethylene (—CH═CH—),propylene (—CH₂—CH═CH—) and butylene (—CH₂—CH═CH—CH₂—).

As used herein, “alkynyl” refers to “an unsaturated hydrocarbon grouphaving at least one site of acetylenic unsaturation (i.e., having atleast one moiety of the formula C≡C. Alkynyl contains only C and H whenunsubstituted. When an alkynyl residue having a specific number ofcarbons is named, all geometric isomers having that number of carbonsare intended to be encompassed and described; thus, for example,“pentynyl” is meant to include n-pentynyl, sec-pentynyl, iso-pentynyl,and tert-pentynyl. Examples of alkynyl may include —C≡CH or —C≡C—CH₃. Insome embodiments, alkynyl may be substituted. Suitable alkynylsubstituents may include, for example, hydroxy, amino, and halo.

As used herein, “aryl” refers to an unsaturated aromatic carbocyclicgroup having a single ring (e.g., phenyl) or multiple condensed rings(e.g., naphthyl or anthryl), which condensed rings may or may not bearomatic. Aryl contains only C and H when unsubstituted. An aryl grouphaving more than one ring where at least one ring is non-aromatic may beconnected to the parent structure at either an aromatic ring position orat a non-aromatic ring position. In one variation, an aryl group havingmore than one ring where at least one ring is non-aromatic is connectedto the parent structure at an aromatic ring position. Examples of arylmay include phenyl, phenol, and benzyl. In some embodiments, aryl may besubstituted. Suitable aryl substituents may include, for example, alkyl,alkenyl, alkynyl, hydroxy, amino, and halo.

As used herein, “arylene” refers to the same residues as aryl, buthaving bivalency.

As used herein, “cycloalkyl” includes a carbocyclic, non-aromatic groupthat is connected via a ring carbon atom, which contains only C and Hwhen unsubstituted. The cycloalkyl can consist of one ring, such ascyclohexyl, or multiple rings, such as adamantyl. A cycloalkyl with morethan one ring may be fused, spiro or bridged, or combinations thereof.Examples of cycloalkyl groups include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, adamantyl, and decahydronaphthalenyl. In someembodiments, cycloalkyl may be substituted. Suitable cycloalkylsubstituents may include, for example, alkyl, hydroxy, amino, and halo.

As used herein, “cycloalkylene” refers to the same residues ascycloalkyl, but having bivalency.

As used herein, “heteroaryl” refers to an unsaturated aromaticcarbocyclic group having from 1 to 10 annular carbon atoms and at leastone annular heteroatom, including but not limited to heteroatoms such asnitrogen, oxygen and sulfur. A heteroaryl group may have a single ring(e.g., pyridyl, pyridinyl, imidazolyl) or multiple condensed rings(e.g., indolizinyl, benzothienyl) which condensed rings may or may notbe aromatic. A heteroaryl group having more than one ring where at leastone ring is non-aromatic may be connected to the parent structure ateither an aromatic ring position or at a non-aromatic ring position. Inone variation, a heteroaryl group having more than one ring where atleast one ring is non-aromatic is connected to the parent structure atan aromatic ring position. Examples of heteroaryls may include pyridyl,pyridinyl, imidazolyl, and thiazolyl. In some embodiments, heteroarylmay be substituted. Suitable heteroaryl substituents may include, forexample, alkyl, alkenyl, alkynyl, hydroxy, amino, and halo.

As used herein, “heteroarylene” refers to the same residues asheteroaryl, but having bivalency.

It should be understood that the alkyl, cycloalkyl, alkenyl, alkynyl,aryl, heteroaryl, ether, ester, and carbamate may be substituted, wherethe particular group or groups being described may have no non-hydrogensubstituents, or the group or groups may have one or more non-hydrogensubstituents. If not otherwise specified, the total number of suchsubstituents that may be present is equal to the number of H atomspresent on the unsubstituted form of the group being described.

Polymeric Acid Catalysts

In one aspect, the polymeric acid catalysts provided herein are polymersmade up of acidic monomers and ionic monomers (which are also known as“ionomers) connected to form a polymeric backbone. Each acidic monomerincludes at least one Bronsted-Lowry acid, and each ionic monomerincludes at least one nitrogen-containing cationic group orphosphorous-containing cationic group. Some of the acidic and ionicmonomers may also include a linker that connects the Bronsted-Lowry acidand cationic group, respectively, to the polymeric backbone. For theacidic monomers, the Bronsted-Lowry acid and the linker together form aside chain. Similarly, for the ionic monomers, the cationic group andthe linker together form a side chain. With reference to the portion ofthe exemplary polymer depicted in FIG. 1, the side chains are pendantfrom the polymeric backbone.

a) Acidic and Ionic Monomers

The polymers described herein contain monomers that have at least oneBronsted-Lowry acid and at least one cationic group. The Bronsted-Lowryacid and the cationic group may be on different monomers or on the samemonomer.

In some embodiments, the acidic monomers may have one Bronsted-Lowryacid. In other embodiments, the acidic monomers may have two or moreBronsted-Lowry acids, as is chemically feasible. When the acidicmonomers have two or more Bronsted-Lowry acids, the acids may be thesame or different.

Suitable Bronsted-Lowry acids may include any Bronsted-Lowry acid thatcan form a covalent bond with a carbon. The Bronsted-Lowry acids mayhave a pK value of less than about 7, less than about 6, less than about5, less than about 4, less than about 3, less than about 2, less thanabout 1, or less than zero. In some embodiments, the Bronsted-Lowry acidat each occurrence may be independently selected from sulfonic acid,phosphonic acid, acetic acid, isophthalic acid, boronic acid, andperfluorinated acid.

The acidic monomers in the polymer may either all have the sameBronsted-Lowry acid, or may have different Bronsted-Lowry acids. In anexemplary embodiment, each Bronsted-Lowry acid in the polymer issulfonic acid. In another exemplary embodiment, each Bronsted-Lowry acidin the polymer is phosphonic acid. In yet another exemplary embodiment,the Bronsted-Lowry acid in some monomers of the polymer is sulfonicacid, while the Bronsted-Lowry acid in other monomers of the polymer isphosphonic acid.

In some embodiments, the ionic monomers may have one cationic group. Inother embodiments, the ionic monomers may have two or more cationicgroups, as is chemically feasible. When the ionic monomers have two ormore cationic groups, the cationic groups may be the same or different.

Suitable cationic groups may include any nitrogen-containing cationicgroup or a phosphorus-containing cationic group. In some embodiments,the nitrogen-containing cationic group at each occurrence may beindependently selected from ammonium, pyrrolium, imidazolium,pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium,pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, andpyrollizinium. In other embodiments, the phosphorous-containing cationicgroup at each occurrence may be independently selected from triphenylphosphonium, trimethyl phosphonium, triethyl phosphonium, tripropylphosphonium, tributyl phosphonium, trichloro phosphonium, and trifluorophosphonium.

The ionic monomers may either all have the same cationic group, or mayhave different cationic groups. In some embodiments, each cationic groupin the polymer is a nitrogen-containing cationic group. In otherembodiments, each cationic group in the polymer is aphosphorous-containing cationic group. In yet other embodiments, thecationic group in some monomers of the polymer is a nitrogen-containingcationic group, whereas the cationic group in other monomers of thepolymer is a phosphorous-containing cationic group. In an exemplaryembodiment, each cationic group in the polymer is imidazolium. Inanother exemplary embodiment, the cationic group in some monomers of thepolymer is imidazolium, while the cationic group in other monomers ofthe polymer is pyridinium. In yet another exemplary embodiment, eachcationic group in the polymer is a substituted phosphonium. In yetanother exemplary embodiment, the cationic group in some monomers of thepolymer is triphenyl phosphonium, while the cationic group in othermonomers of the polymer is imidazolium.

In some embodiments, the cationic group may coordinate with acounterion. For example, the counterion may be a halide (e.g., bromide,chloride, iodide, and fluoride), nitrate (NO₃ ⁻), sulfate (SO₄ ²⁻),formate (HCOO⁻), acetate (H₃COO⁻), or an organosulfonate (R—SO₃ ⁻; whereR is an organic functional group, e.g., methyl, phenyl).

In other embodiments, the cationic group may coordinate with aBronsted-Lowry acid in the polymer. At least a portion of theBronsted-Lowry acids and the cationic groups in the polymer may forminter-monomer ionic associations. Inter-monomeric ionic associationsresult in salts forming between monomers in the polymer, rather thanwith external counterions. In some exemplary embodiments, the ratio ofacidic monomers engaged in inter-monomer ionic associations to the totalnumber of acidic monomers may be at most 90% internally-coordinated, atmost 80% internally-coordinated, at most 70% internally-coordinated, atmost 60% internally-coordinated, at most 50% internally-coordinated, atmost 40% internally-coordinated, at most 30% internally-coordinated, atmost 20% internally-coordinated, at most 10% internally-coordinated, atmost 5% internally-coordinated, at most 1% internally-coordinated, orless than 1% internally-coordinated. It should be understood thatinternally-coordinates sites are less likely to exchange with an ionicsolution that is brought into contact with the polymer.

Some of the monomers in the polymer contain both the Bronsted-Lowry acidand the cationic group in the same monomer. Such monomers are referredto as “acidic-ionic monomers”. In exemplary embodiments, a side chain ofan acidic-ionic monomer may contain imidazolium and acetic acid, orpyridinium and boronic acid.

With reference to the portion of an exemplary polymer depicted in FIG.2, the Bronsted-Lowry acid and the cationic group in the side chains ofthe monomers may be directly connected to the polymeric backbone orconnected to the polymeric backbone by a linker.

Suitable linkers may include, for example, unsubstituted or substitutedalkylene, unsubstituted or substituted cycloalkylene, unsubstituted orsubstituted alkenylene, unsubstituted or substituted arylene,unsubstituted or substituted heteroarylene, unsubstituted or substitutedalkylene ether, unsubstituted or substituted alkylene ester, andunsubstituted or substituted alkylene carbamate. In some embodiments,the linker is an unsubstituted or substituted C5 or C6 arylene. Incertain embodiments, the linker is an unsubstituted or substitutedphenylene. In one exemplary embodiment, the linker is unsubstitutedphenylene. In another exemplary embodiment, the linker is substitutedphenylene (e.g., hydroxy-substituted phenylene).

Further, it should be understood that some or all of the acidic monomersconnected to the polymeric backbone by a linker may have the samelinker, or independently have different linkers. Similarly, some or allof the ionic monomers connected to the polymeric backbone by a linkermay have the same linker, or independently have different linkers.Further, some or all of the acidic monomers connected to the polymericbackbone by a linker may have the same or different linkers as some orall of the ionic monomers connected to the polymeric backbone by alinker.

In certain embodiments, the acidic monomers may have a side chain with aBronsted-Lowry acid that is connected to the polymeric backbone by alinker. Side chains with one or more Bronsted-Lowry acids connected by alinker may include, for example,

As used herein,

denotes the point of attachment to the polymeric backbone.

In other embodiments, the acidic monomers may have a side chain with aBronsted-Lowry acid that is directly connected to the polymericbackbone. Side chains with a Bronsted-Lowry acid directly connected tothe polymer backbone may include, for example,

In certain embodiments, the ionic monomers may have a side chain with acationic group that is connected to the polymeric backbone by a linker.Side chains with one or more cationic groups connected by a linker mayinclude, for example,

In other embodiments, the ionic monomers may have a side chain with acationic group that is directly connected to the polymeric backbone.Side chains with a nitrogen-containing cationic group directly connectedto the polymeric backbone may include, for example,

Side chains with a phosphorous-containing cationic group directlyconnected to the polymeric backbone may include, for example,

In other embodiments, the monomers may have a side chain containing botha Bronsted-Lowry acid and a cationic group, where either theBronsted-Lowry acid is connected to the polymeric backbone by a linkeror the cationic group is connected to the polymeric backbone by alinker. Monomers that have side chains containing both a Bronsted-Lowryacid and a cationic group may also be called “acidic ionomers”. Suchside chains in acidic-ionic monomers that are connected by a linker mayinclude, for example,

In other embodiments, the monomers may have a side chain containing botha Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowryacid is directly connected to the polymeric backbone, the cationic groupis directly connected to the polymeric backbone, or both theBronsted-Lowry acid and the cationic group are directly connected to thepolymeric backbone. Such side chains in acidic-ionic monomers mayinclude, for example,

In some embodiments, the acidic and ionic monomers make up a substantialportion of the polymer. In certain embodiments, the acidic and ionicmonomers make up at least about 30%, at least about 40%, at least about50%, at least about 60%, at least about 70%, at least about 80%, atleast about 90%, at least about 95%, or at least about 99% of themonomers of the polymer, based on the ratio of the number of acidic andionic monomers to the total number of monomers present in the polymer.

The ratio of the total number of acidic monomers to the total number ofionic monomers may be varied to tune the strength of the acid catalyst.In some embodiments, the total number of acidic monomers exceeds thetotal number of ionic monomers in the polymer. In other embodiments, thetotal number of acidic monomers is at least 2, at least 3, at least 4,at least 5, at least 6, at least 7, at least 8, at least 9 or at least10 times the total number of ionic monomers in the polymer. In certainembodiments, the ratio of the total number of acidic monomers to thetotal number of ionic monomers is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1,8:1, 9:1 or 10:1.

In some embodiments, the total number of ionic monomers exceeds thetotal number of acidic monomers in the polymer. In other embodiments,the total number of ionic monomers is at least 2, at least 3, at least4, at least 5, at least 6, at least 7, at least 8, at least 9 or atleast 10 times the total number of acidic monomers in the polymer. Incertain embodiments, the ratio of the total number of ionic monomers tothe total number of acidic monomers is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1,7:1, 8:1, 9:1 or 10:1.

The polymers described herein may be characterized by the chemicalfunctionalization of the polymer. In some embodiments, the polymer mayhave between 0.1 and 20 mmol, between 0.1 and 15 mmol, between 0.01 and12 mmol, between 0.01 and 10 mmol, between 1 and 8 mmol, between 2 and 7mmol, between 3 and 6 mmol, between 1 and 5, or between 3 and 5 mmol ofthe Bronsted-Lowry acid per gram of the polymer. In particularembodiments where the polymer has at least some monomers with sidechains having sulfonic acid as the Bronsted-Lowry acid, the polymer mayhave between 0.05 to 10 mmol of the sulfonic acid per gram of thepolymer. In other embodiments where the polymer has at least somemonomers with side chains having phosphonic acid as the Bronsted-Lowryacid, the polymer may have between 0.01 and 12 mmol of the phosphonicacid per gram of the polymer. In other embodiments where the polymer hasat least some monomers with side chains having acetic acid as theBronsted-Lowry acid, the polymer may have between 0.01 and 12 mmol ofthe acetic acid per gram of the polymer. In other embodiments where thepolymer has at least some monomers with side chains having isophthalicacid as the Bronsted-Lowry acid, the polymer may have between 0.01 and 5mmol of the isophthalic acid per gram of the polymer. In otherembodiments where the polymer has at least some monomers with sidechains having boronic acid as the Bronsted-Lowry acid, the polymer mayhave between 0.01 and 20 mmol of the boronic acid per gram of thepolymer. In other embodiments where the polymer has at least somemonomers with side chains having perfluorinated acid as theBronsted-Lowry acid, the polymer may have between 0.01 and 5 mmol of theperfluorinated acid per gram of the polymer.

In some embodiments, the polymer may have between 0.01 and 10 mmol,between 0.01 and 8.0 mmol, between 0.01 and 4 mmol, between 1 and 10mmol, between 2 and 8 mmol, or between 3 and 6 mmol of the ionic group.In such embodiments, the ionic group includes the cationic group listed,as well as any suitable counterion described herein (e.g., halide,nitrate, sulfate, formate, acetate, or organosulfonate). In particularembodiments where the polymer has at least some monomers with sidechains having imidazolium as part of the ionic group, the polymer mayhave between 0.01 and 8 mmol of the ionic group per gram of the polymer.In other embodiments where the polymer has at least some monomers withside chains having pyridinium as part of the ionic group, the polymermay have between 0.01 and 8 mmol of the ionic group per gram of thepolymer. In other embodiments where the polymer has at least somemonomers with side chains having triphenyl phosphonium as part of theionic group, the polymer may have between 0.01 and 4 mmol of the ionicgroup per gram of the polymer.

b) Hydrophobic Monomers

The polymers described herein may further include monomers having a sidechain containing a non-functional group, such as a hydrophobic group. Insome embodiments, the hydrophobic group is connected directly to thepolymeric backbone. Suitable hydrophobic groups may include, forexample, unsubstituted or substituted alkyl, unsubstituted orsubstituted cycloalkyl, unsubstituted or substituted aryl, orunsubstituted or substituted heteroaryl. In some embodiments, thehydrophobic group is unsubstituted or substituted C5 or C6 aryl. Incertain embodiments, the hydrophobic group is unsubstituted orsubstituted phenyl. In one exemplary embodiment, the hydrophobic groupis unsubstituted phenyl. Further, it should be understood that thehydrophobic monomers may either all have the same hydrophobic group, ormay have different hydrophobic groups.

c) Arrangement of Monomers

In some embodiments, the acidic monomers, the ionic monomers, theacidic-ionic monomers and the hydrophobic monomers, where present, maybe arranged in alternating sequence or in a random order as blocks ofmonomers. In some embodiments, each block has not more than twenty,fifteen, ten, six, or three monomers.

In some embodiments, the polymer is randomly arranged in an alternatingsequence. With reference to the portion of the exemplary polymerdepicted in FIG. 3A, the monomers are randomly arranged in analternating sequence.

In other embodiments, the polymer is randomly arranged as blocks ofmonomers. With reference to the portion of the exemplary polymerdepicted in FIG. 3B, the monomers are arranged in blocks of monomers.

The polymers described herein may also be cross-linked. Suchcross-linked polymers may be prepared by introducing cross-linkinggroups. In some embodiments, cross-linking may occur within a givenpolymeric chain, with reference to the portion of the exemplary polymersdepicted in FIGS. 4A and 4B. In other embodiments, cross-linking mayoccur between two or more polymeric chains, with reference to theportion of the exemplary polymers in FIGS. 5A, 5B, 5C and 5D.

With reference to FIGS. 4A, 4B and 5A, it should be understood that R¹,R² and R³, respectively, are exemplary cross linking groups. Suitablecross-linking groups that may be used to form a cross-linked polymerwith the polymers described herein include, for example, substituted orunsubstituted divinyl alkanes, substituted or unsubstituted divinylcycloalkanes, substituted or unsubstituted divinyl aryls, substituted orunsubstituted heteroaryls, dihaloalkanes, dihaloalkenes, dihaloalkynes.For example, cross-linking groups may include divinylbenzene,diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane,divinylethane, dichloroethane, divinylpropane, dichloropropane,divinylbutane, dichlorobutane, ethylene glycol, and resorcinol.

d) Polymeric Backbone

The polymeric backbone described herein may include, for example,polyalkylenes, polyalkenyl alcohols, polycarbonate, polyarylenes,polyaryletherketones, and polyamide-imides. In certain embodiments, thepolymeric backbone may be selected from polyethylene, polypropylene,polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride,polyphenol-aldehyde, polytetrafluoroethylene, polybutyleneterephthalate, polycaprolactam, and poly(acrylonitrile butadienestyrene).

With reference to FIG. 6A, in one exemplary embodiment, the polymericbackbone is polyethylene. With reference to FIG. 6B, in anotherexemplary embodiment, the polymeric backbone is polyvinyl alcohol.

The polymeric backbone described herein may also include an ionic groupintegrated as part of the polymeric backbone. Such polymeric backbonesmay also be called “ionomeric backbones”. In certain embodiments, thepolymeric backbone may be selected from polyalkyleneammonium,polyalkylenediammonium, polyalkylenepyrrolium, polyalkyleneimidazolium,polyalkylenepyrazolium, polyalkyleneoxazolium, polyalkylenethiazolium,polyalkylenepyridinium, polyalkylenepyrimidinium,polyalkylenepyrazinium, polyalkylenepyradizimium,polyalkylenethiazinium, polyalkylenemorpholinium,polyalkylenepiperidinium, polyalkylenepiperizinium,polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,polyalkylenetrimethylphosphonium, polyalkylenetriethylphosphonium,polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium,polyalkylenetrichlorophosphonium, polyalkylenetrifluorophosphonium, andpolyalkylenediazolium.

With reference to FIG. 6C, in yet another exemplary embodiment, thepolymeric backbone is a polyalkyleneimidazolium.

Further, the number of atoms between side chains in the polymericbackbone may vary. In some embodiments, there are between zero andtwenty atoms, zero and ten atoms, or zero and six atoms, or zero andthree atoms between side chains attached to the polymeric backbone. Withreference to FIG. 7A, in one exemplary embodiment, there are threecarbon atoms between the side chain with the Bronsted-Lowry acid and theside chain with the cationic group. In another example, with referenceto FIG. 7B, there are zero atoms between the side chain with the acidicmoiety and the side chain with the ionic moiety.

It should be understood that the polymers may include any of theBronsted-Lowry acids, cationic groups, counterions, linkers, hydrophobicgroups, cross-linking groups, and polymeric backbones described herein,as if each and every combination were listed separately. For example, inone embodiment, the polymer may include benzenesulfonic acid (i.e., asulfonic acid with a phenyl linker) connected to a polystyrene backbone,and an imidazolium chloride connected directly to the polystyrenebackbone. In another embodiment, the polymer may includeboronyl-benzyl-pyridinium chloride (i.e., a boronic acid and pyridiniumchloride in the same monomer unit with a phenyl linker) connected to apolystyrene backbone. In yet another embodiment, the polymer may includebenzenesulfonic acid and an imidazolium sulfate moiety each individuallyconnected to a polyvinyl alcohol backbone.

Exemplary polymers described herein include:

-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    nitrate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    nitrate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    iodide-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bromide-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-ium    formate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-nitrate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bromide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-iodide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium    formate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triphenyl-(4-vinylbenzyl)-phosphonium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-triethyl-(4-vinylbenzyl)-ammonium    acetate-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-4-boronyl-1-(4-vinylbenzyl)-pyridinium    chloride-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    nitrate-co-1-(4-vinylphenyl)methylphosphonic    acid-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridinium    acetate-co-divinylbenzene];-   poly[styrene-co-4-vinylbenzenesulfonic    acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene];-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-4-vinylphenylphosphonic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    chloride-co-divinylbenzene];-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    bisulfate-co-divinylbenzene];-   poly[styrene-co-(4-vinylbenzylamino)-acetic    acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium    acetate-co-divinylbenzene];-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    chloride-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenyl phosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium    chloride-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenyl phosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    bisulfate-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium    bisulfate-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenyl phosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium    acetate-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenyl phosphonium    acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium    acetate-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenyl phosphonium    acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenylphosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylmorpholinium    chloride-co-vinylbenzyltriphenylphosphonium    chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylmorpholinium    bisulfate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylmorpholinium    acetate-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene)-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylmethylimidazolium nitrate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenesulfonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium    bisulfate-co-divinylbenzene);-   poly(styrene-co-4-vinylbenzenephosphonic    acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene);-   poly(butyl-vinylimidazolium chloride-co-butylimidazolium    bisulfate-co-4-vinylbenzenesulfonic acid);-   poly(butyl-vinylimidazolium bisulfate-co-butylimidazolium    bisulfate-co-4-vinylbenzenesulfonic acid);-   poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl    alcohol);-   poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic    acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzyl    alcohol).

Properties of the Polymeric Acid Catalysts

The polymers described herein have one or more catalytic properties. Asused herein, a “catalytic property” of a material is a physical and/orchemical property that increases the rate and/or extent of a reactioninvolving the material. The catalytic properties may include at leastone of the following properties: a) disruption of a hydrogen bond incellulosic materials; b) intercalation of the polymeric acid catalystinto crystalline domains of cellulosic materials; and c) cleavage of aglycosidic bond in cellulosic materials. In other embodiments, thepolymeric acid catalysts that have two or more of the catalyticproperties described above, or all three of the catalytic propertiesdescribed above.

In certain embodiments, the polymeric acid catalysts described hereinhave the ability to catalyze a chemical reaction by donation of aproton, and may be regenerated during the reaction process.

In some embodiments, the polymers described herein have a greaterspecificity for cleavage of a glycosidic bond than dehydration of amonosaccharide.

Solid Particles

The polymers described herein may form solid particles. One of skill inthe art would recognize the various known techniques and methods to makesolid particles. For example, a solid particle may be formed through theprocedures of emulsion or dispersion polymerization, which are known toone of skill in the art. In other embodiments, the solid particles maybe formed by grinding or breaking the polymer into particles, which arealso techniques and methods that are known to one of skill in the art.

In certain embodiments, the solid particles are substantially free ofpores. In certain embodiments where the solid particles aresubstantially free of pores, the solid particles contain no more than50%, no more than 40%, no more than 30%, no more than 20%, no more than15%, no more than 10%, no more than 5%, or no more than 1% of pores.Such particles may be advantageous since solvent and soluble species(e.g., sugars) are less likely to permeate into the solid particle.

In other embodiments, the solid particles include a microporous gelresin. In yet other embodiments, the solid particles include amacroporous gel resin.

Other methods known in the art to prepare solid particles includecoating the polymers described herein on the surface of a solid core.The solid core can be a non-catalytic support. Suitable materials forthe solid core may include an inert material (e.g., aluminum oxide, corncob, crushed glass, chipped plastic, pumice, silicon carbide, or walnutshell) or a magnetic material. Polymeric coated core particles can bemade by techniques and methods that are known to one of skill in theart, for example, by dispersion polymerization to grow a cross-linkedpolymer shell around the core material, or by spray coating or melting.

The solid particles coated with the polymer described herein have one ormore catalytic properties. In some embodiments, at least about 50%, atleast 60%, at least 70%, at least 80% or at least 90% of the catalyticactivity of the solid particle is present on or near the exteriorsurface of the solid particle.

This form of the polymeric acid catalysts can be advantageous over othercatalysts known in the art due to, for example, ease of handling. Thesolid nature of the polymeric catalysts can provide for ease ofrecycling (e.g., by filtering the catalyst), without requiringdistillation or extraction methods. For example, the density and size ofthe particle can be selected such that the catalyst particles can beseparated from the materials used in a process for the break-down ofbiomaterials. Particles can be selected based on sedimentation rate,e.g., relative to materials used or produced in a reaction mixture,particle density, or particle size. Alternatively, solid particlescoated with the polymeric acid catalysts that have a magnetically activecore can be recovered by electromagnetic methods known to one of skillin the art.

Saccharification Using the Polymeric Acid Catalysts

In one aspect, provided are methods for saccharification of cellulosicmaterials (e.g., biomass) using the polymeric acid catalysts describedherein. Saccharification refers to the hydrolysis of cellulosicmaterials (e.g., biomass) into one or more sugars, by breaking down thecomplex carbohydrates of cellulose (and hemicellulose, where present) inthe biomass. The one or more sugars may be monosaccharides and/oroligosaccharides. As used herein, “oligosaccharide” refers to a compoundcontaining two or more monosaccharide units linked by glycosidic bonds.In certain embodiments, the one or more sugars are selected fromglucose, cellobiose, xylose, xylulose, arabinose, mannose and galactose.

It should be understood that the cellulosic material may be subjected toa one-step or a multi-step hydrolysis process. For example, in someembodiments, the cellulosic material is first contacted with thepolymeric acid catalyst, and then the resulting product is contactedwith one or more enzymes in a second hydrolysis reaction (e.g., usingenzymes).

The one or more sugars obtained from hydrolysis of cellulosic materialmay be used in a subsequent fermentation process to produce biofuels(e.g., ethanol) and other bio-based chemicals. For example, in someembodiments, the one or more sugars obtained by the methods describedherein may undergo subsequent bacterial or yeast fermentation to producebiofuels and other bio-based chemicals.

Further, it should be understood that any method known in the art thatincludes pretreatment, enzymatic hydrolysis (saccharification),fermentation, or a combination thereof, can be used with the polymericacid catalysts in the methods described herein. The polymeric acidcatalysts may be used before or after pretreatment methods to make thecellulose (and hemicellulose, where present) in the biomass moreaccessible to hydrolysis.

a) Cellulosic Materials

Cellulosic materials may include any material containing celluloseand/or hemicellulose. In certain embodiments, cellulosic materials maybe lignocellulosic materials that contain lignin in addition tocellulose and/or hemicellulose. Cellulose is a polysaccharide thatincludes a linear chain of beta-(1-4)-D-glucose units. Hemicellulose isalso a polysaccharide; however, unlike cellulose, hemicellulose is abranched polymer that typically includes shorter chains of sugar units.Hemicellulose may include a diverse number of sugar monomers including,for example, xylans, xyloglucans, arabinoxylans, and mannans.

Cellulosic materials can typically be found in biomass. In someembodiments, the biomass used with the sold polymeric acid catalystsdescribed herein contains a substantial proportion of cellulosicmaterial, such as 5%, 10%, 15%, 20%, 25%, 50%, 75%, 90% or greater than90% cellulose. In some embodiments, cellulosic materials may includeherbaceous materials, agricultural residues, forestry residues,municipal solid waste, waste paper, and pulp and paper mill residues. Incertain embodiments, the cellulosic material is corn stover, corn fiber,or corn cob. In other embodiments, the cellulosic material is bagasse,rice straw, wheat straw, switch grass or miscanthus. In yet otherembodiments, cellulosic material may also include chemical cellulose(e.g., Avicel®), industrial cellulose (e.g., paper or paper pulp),bacterial cellulose, or algal cellulose. As described herein and knownin the art, the cellulosic materials may be used as obtained from thesource, or may be subjected to one or pretreatments. For example,pretreated corn stover (“PCS”) is a cellulosic material derived fromcorn stover by treatment with heat and/or dilute sulfuric acid, and issuitable for use with the polymeric acid catalysts described herein.

Several different crystalline structures of cellulose are known in theart. For example, with reference to FIG. 8, crystalline cellulose areforms of cellulose where the linear beta-(1-4)-glucan chains may bepacked into a three-dimensional superstructure. The aggregatedbeta-(1-4)-glucan chains are typically held together via inter- andintra-molecular hydrogen bonds. Steric hindrance resulting from thestructure of crystalline cellulose may impede access of the reactivespecies, such as enzymes or chemical catalysts, to the beta-glycosidicbonds in the glucan chains. In contrast, non-crystalline cellulose andamorphous cellulose are forms of cellulose in which individualbeta-(1-4)-glucan chains are not appreciably packed into ahydrogen-bonded super-structure, where access of reactive species to thebeta-glycosidic bonds in the cellulose is hindered.

One of skill in the art would recognize that natural sources ofcellulose may include a mixture of crystalline and non-crystallinedomains. The regions of a beta-(1-4)-glucan chain where the sugar unitsare present in their crystalline form are referred to herein as the“crystalline domains” of the cellulosic material. Generally, thebeta-(1-4)-glucan chains present in natural cellulose exhibit a numberaverage degree of polymerization between 1,000 and 4,000 anhydroglucose(“AHG”) units (i.e., 1,000-4,000 glucose molecules linked viabeta-glycosidic bonds), while the number average degree ofpolymerization for the crystalline domains is typically between 200 and300 AHG units. See e.g., R. Rinaldi, R. Palkovits, and F. Schüth, Angew.Chem. Int. Ed., 47, 8047-8050 (2008); Y.-H. P. Zhang and L. R. Lynd,Biomacromolecules, 6, 1501-1515 (2005).

Typically, cellulose has multiple crystalline domains that are connectedby non-crystalline linkers that may include a small number ofanhydroglucose units. One of skill in the art would recognize thattraditional methods to digest biomass, such as dilute acidic conditions,may digest the non-crystalline domains of natural cellulose, but not thecrystalline domains. Dilute acid treatment does not appreciably disruptthe packing of individual beta-(1-4)-glucan chains into ahydrogen-bonded super-structure, nor does it hydrolyze an appreciablenumber of glycosidic bonds in the packed beta-(1-4)-glucan chains.Consequently, treatment of natural cellulosic materials with dilute acidreduces the number average degree of polymerization of the inputcellulose to approximately 200-300 anhydroglucose units, but does notfurther reduce the degree of polymerization of the cellulose to below150-200 anhydroglucose units (which is the typical size of thecrystalline domains).

In certain embodiments, the polymeric acid catalysts described hereinmay be used to digest natural cellulosic materials. The polymeric acidcatalysts may be used to digest crystalline cellulose by a chemicaltransformation in which the average degree of polymerization ofcellulose is reduced to a value less than the average degree ofpolymerization of the crystalline domains. Digestion of crystallinecellulose can be detected by observing reduction of the average degreeof polymerization of cellulose. In certain embodiments, the polymericacid catalysts can reduce the average degree of polymerization ofcellulose from at least 300 AGH units to less than 200 AHG units.

It should be understood that the polymeric acid catalysts describedherein may be used to digest crystalline cellulose, as well asmicrocrystalline cellulose. One of skill in the art would recognize thatcrystalline cellulose typically has a mixture of crystalline andamorphous or non-crystalline domains, whereas microcrystalline cellulosetypically refers to a form of cellulose where the amorphous ornon-crystalline domains have been removed by chemical processing suchthat the residual cellulose substantially has only crystalline domains.

b) Pretreatment of Cellulosic Materials

In some embodiments, the polymeric acid catalysts described herein maybe used with cellulosic materials that have been pretreated. In otherembodiments, the polymeric acid catalysts described herein may be usedwith cellulosic materials before pretreatment.

Any pretreatment process known in the art can be used to disrupt plantcell wall components of cellulosic material, including, for example,chemical or physical pretreatment processes. See, e.g., Chandra et al.,Substrate pretreatment: The key to effective enzymatic hydrolysis oflignocellulosics?, Adv. Biochem. Engin./Biotechnol., 108: 67-93 (2007);Galbe and Zacchi, Pretreatment of lignocellulosic materials forefficient bioethanol production, Adv. Biochem. Engin./Biotechnol., 108:41-65 (2007); Hendriks and Zeeman, Pretreatments to enhance thedigestibility of lignocellulosic biomass, Bioresource Technol., 100:10-18 (2009); Mosier et al., Features of promising technologies forpretreatment of lignocellulosic biomass, Bioresource Technol., 96:673-686 (2005); Taherzadeh and Karimi, Pretreatment of lignocellulosicwastes to improve ethanol and biogas production: A review, Int. J. ofMol. Sci., 9: 1621-1651 (2008); Yang and Wyman, Pretreatment: the key tounlocking low-cost cellulosic ethanol, Biofuels Bioproducts andBiorefining (Biofpr), 2: 26-40 (2008). Examples of suitable pretreatmentmethods are described by Schell et al. (Appl. Biochem. and Biotechnol.,105-108: 69-85 (2003) and Mosier et al. (Bioresource Technol., 96:673-686 (2005), and in U.S. Patent Application No. 2002/0164730.

In other embodiments, the polymeric acid catalysts described herein maybe used with cellulosic materials that have not been pretreated.Further, the cellulosic material can also be subjected to otherprocesses instead of or in addition to pretreatment including, forexample, particle size reduction, pre-soaking, wetting, washing, orconditioning.

Moreover, the use of the term “pretreatment” does not imply or requireany specific timing of the steps of the methods described herein. Forexample, the cellulosic material can be pretreated before hydrolysis.Alternatively, the pretreatment can be carried out simultaneously withhydrolysis. In some embodiments, the pretreatment step itself results insome conversion of biomass to sugars (for example, even in the absenceof the polymeric acid catalysts described herein).

Several common methods that may be used to pretreat cellulose materialsfor use with the polymeric acid catalysts are described below.

Steam Pretreatment

Cellulosic material is heated to disrupt the plant cell wall components(e.g., lignin, hemicellulose, cellulose) to make the cellulose and/orhemicellulose more accessible to enzymes. Cellulosic material istypically passed to or through a reaction vessel, where steam isinjected to increase the temperature to the required temperature andpressure is retained therein for the desired reaction time.

In certain embodiments where steam pretreatment is employed to pretreatthe cellulosic materials, the pretreatment can be performed at atemperature between 140° C. and 230° C., between 160° C. and 200° C., orbetween 170° C. and 190° C. It should be understood, however, that theoptimal temperature range for steam pretreatment may vary depending onthe polymeric acid catalyst used.

In certain embodiments, the residence time for the steam pretreatment is1 to 15 minutes, 3 to 12 minutes, or 4 to 10 minutes. It should beunderstood, however, that the optimal residence time for steampretreatment may vary depending on the temperature range and thepolymeric acid catalyst used.

In some embodiments, steam pretreatment can be combined with anexplosive discharge of the material after the pretreatment, which isknown as steam explosion—a rapid flashing to atmospheric pressure andturbulent flow of the material to increase the accessible surface areaby fragmentation. See Duff and Murray, Bioresource Technol., 855: 1-33(1996); Galbe and Zacchi, Appl. Microbiol. Biotechnol., 59: 618-628(2002); U.S. Patent Application No. 2002/0164730.

During steam pretreatment, acetyl groups in hemicellulose can becleaved, and the resulting acid can autocatalyze the partial hydrolysisof the hemicellulose to monosaccharides and/or oligosaccharides. One ofskill in the art would recognize, however, that lignin (when present inthe cellulosic material) is removed to only a limited extent. Thus, incertain embodiments, a catalyst such as sulfuric acid (typically 0.3% to3% w/w) may be added prior to steam pretreatment, to decrease the timeand temperature, increase the recovery, and improve enzymatichydrolysis. See Ballesteros et al., Appl. Biochem. Biotechnol., 129-132:496-508 (2006); Varga et al., Appl. Biochem. Biotechnol., 113-116:509-523 (2004); Sassner et al., Enzyme Microb. Technol., 39: 756-762(2006).

Chemical Pretreatment

Chemical pretreatment of cellulosic materials can promote the separationand/or release of cellulose, hemicellulose, and/or lignin by chemicalprocesses. Examples of suitable chemical pretreatment processes include,for example, dilute acid pretreatment, lime pretreatment, wet oxidation,ammonia fiber/freeze explosion (AFEX), ammonia percolation (APR), andorganosolvent pretreatments.

In one embodiment, dilute or mild acid pretreatment is employed.Cellulosic material may be mixed with a dilute acid and water to form aslurry, heated by steam to the desired temperature, and after aresidence time flashed to atmospheric pressure. Suitable acids for thispretreatment method may include, for example, sulfuric acid, aceticacid, citric acid, nitric acid, phosphoric acid, tartaric acid, succinicacid, hydrogen chloride, or mixtures thereof. In one preferredvariation, sulfuric acid is used. The dilute acid treatment may beconducted in a pH range of 1-5, a pH range of 1-4, or a pH range of 1-3.The acid concentration may be in the range from 0.01 to 20 wt % acid,0.05 to 10 wt % acid, 0.1 to 5 wt % acid, or 0.2 to 2.0 wt % acid. Theacid is contacted with cellulosic material, and may be held at atemperature in the range of 160-220° C., or 165-195° C., for a period oftime ranging from seconds to minutes (e.g., 1 second to 60 minutes). Thedilute acid pretreatment can be performed with a number of reactordesigns, including for example plug-flow reactors, counter-currentreactors, and continuous counter-current shrinking bed reactors. SeeDuff and Murray (1996), supra; Schell et al., Bioresource Technol., 91:179-188 (2004); Lee et al., Adv. Biochem. Eng. Biotechnol., 65: 93-115(1999).

In another embodiment, an alkaline pretreatment may be employed.Examples of suitable alkaline pretreatments include, for example, limepretreatment, wet oxidation, ammonia percolation (APR), and ammoniafiber/freeze explosion (AFEX). Lime pretreatment may be performed withcalcium carbonate, sodium hydroxide, or ammonia at temperatures of 85°C. to 150° C., and at residence times from 1 hour to several days. SeeWyman et al., Bioresource Technol., 96: 1959-1966 (2005); Mosier et al.,Bioresource Technol., 96: 673-686 (2005).

In yet another embodiment, wet oxidation may be employed. Wet oxidationis a thermal pretreatment that may be performed, for example, at 180° C.to 200° C. for 5-15 minutes with addition of an oxidative agent such ashydrogen peroxide or over-pressure of oxygen. See Schmidt and Thomsen,Bioresource Technol., 64: 139-151 (1998); Palonen et al., Appl. Biochem.Biotechnol., 117: 1-17 (2004); Varga et al., Biotechnol. Bioeng., 88:567-574 (2004); Martin et al., J. Chem. Technol. Biotechnol., 81:1669-1677 (2006). Wet oxidation may be performed, for example, at 1-40%dry matter, 2-30% dry matter, or 5-20% dry matter, and the initial pHmay also be increased by the addition of alkali (e.g., sodiumcarbonate). A modification of the wet oxidation pretreatment method,known as wet explosion—a combination of wet oxidation and steamexplosion, can handle dry matter up to 30%. In wet explosion, theoxidizing agent may be introduced during pretreatment after a certainresidence time, and the pretreatment may end by flashing to atmosphericpressure. See WO 2006/032282.

In yet another embodiment, pretreatment methods using ammonia may beemployed. See e.g., WO 2006/110891; WO 2006/11899; WO 2006/11900; and WO2006/110901. For example, ammonia fiber explosion (AFEX) involvestreating cellulosic material with liquid or gaseous ammonia at moderatetemperatures (e.g., 90-100° C.) and at high pressure (e.g., 17-20 bar)for a given duration (e.g., 5-10 minutes), where the dry matter contentcan be in some instances as high as 60%. See Gollapalli et al., Appl.Biochem. Biotechnol., 98: 23-35 (2002); Chundawat et al., Biotechnol.Bioeng., 96: 219-231 (2007); Alizadeh et al., Appl. Biochem.Biotechnol., 121: 1133-1141 (2005); Teymouri et al., BioresourceTechnol., 96: 2014-2018 (2005). AFEX pretreatment may depolymerizecellulose, partial hydrolyze hemicellulose, and, in some instances,cleave some lignin-carbohydrate complexes.

Organosolvent Pretreatment

An organosolvent solution may be used to delignify cellulosic material.In one embodiment, an organosolvent pretreatment involves extractionusing aqueous ethanol (e.g., 40-60% ethanol) at an elevated temperature(e.g., 160-200° C.) for a period of time (e.g., 30-60 minutes). See Panet al., Biotechnol. Bioeng., 90: 473-481 (2005); Pan et al., Biotechnol.Bioeng., 94: 851-861 (2006); Kurabi et al., Appl. Biochem. Biotechnol.,121: 219-230 (2005). In one variation, sulfuric acid is added to theorganosolvent solution as a catalyst to delignify the cellulosicmaterial. One of skill in the art would recognize that an organosolventpretreatment can typically breakdown the majority of hemicellulose.

Physical Pretreatment

Physical pretreatment of cellulosic materials can promote the separationand/or release of cellulose, hemicellulose, and/or lignin by physicalprocesses. Examples of suitable physical pretreatment processes mayinvolve irradiation (e.g., microwave irradiation), steaming/steamexplosion, hydrothermolysis, and combinations thereof.

Physical pretreatment can involve high pressure and/or high temperature.In one embodiment, the physical pretreatment is steam explosion. In somevariations, high pressure refers to a pressure in the range of 300-600psi, 350-550 psi, or 400-500 psi, or about 450 psi. In some variations,high temperature refers to temperatures in the range of 100-300° C., or140-235° C.

In another embodiment, the physical pretreatment is a mechanicalpretreatment. Suitable examples of mechanical pretreatment may includevarious types of grinding or milling (e.g., dry milling, wet milling, orvibratory ball milling). In some variations, mechanical pretreatment isperformed in a batch-process, such as in a steam gun hydrolyzer systemthat uses high pressure and high temperature (e.g., a Sunds Hydrolyzeravailable from Sunds Defibrator AB, Sweden).

Combined Physical and Chemical Pretreatment

In some embodiments, cellulosic material can be pretreated bothphysically and chemically. For instance, in one variation, thepretreatment step can involve dilute or mild acid treatment and hightemperature and/or pressure treatment. It should be understood that thephysical and chemical pretreatments can be carried out sequentially orsimultaneously. In other variation, the pretreatment may also include amechanical pretreatment, in addition to chemical pretreatment.

Biological Pretreatment

Biological pretreatment techniques can involve applyinglignin-solubilizing microorganisms. See, e.g., Hsu, T.-A., Pretreatmentof Biomass, in Handbook on Bioethanol: Production and Utilization,Wyman, C. E., ed., Taylor & Francis, Washington, D.C., 179-212 (1996);Ghosh and Singh, Physicochemical and biological treatments forenzymatic/microbial conversion of cellulosic biomass, Adv. Appl.Microbiol., 39: 295-333 (1993); McMillan, J. D., Pretreatinglignocellulosic biomass: a review, in Enzymatic Conversion of Biomassfor Fuels Production, Himmel, M. E., Baker, J. O., and Overend, R. P.,eds., ACS Symposium Series 566, American Chemical Society, Washington,D.C., chapter 15 (1994); Gong, C. S., Cao, N. J., Du, J., and Tsao, G.T., Ethanol production from renewable resources, in Advances inBiochemical Engineering/Biotechnology, Scheper, T., ed., Springer-VerlagBerlin Heidelberg, Germany, 65: 207-241 (1999); Olsson andHahn-Hagerdal, Fermentation of lignocellulosic hydrolysates for ethanolproduction, Enz. Microb. Tech., 18: 312-331 (1996); and Vallander andEriksson, Production of ethanol from lignocellulosic materials: State ofthe art, Adv. Biochem. Eng./Biotechnol., 42: 63-95 (1990). In someembodiments, pretreatment may be performed in an aqueous slurry. Inother embodiments, the cellulosic material is present duringpretreatment in amounts between 10-80 wt %, between 20-70 wt %, orbetween 30-60 wt %, or about 50 wt %. Furthermore, after pretreatment,the pretreated cellulosic material can be unwashed or washed using anymethod known in the art (e.g., washed with water) before hydrolysis toproduce one or more sugars or use with the polymeric acid catalyst.

c) Saccharification

Saccharification is typically performed in stirred-tank reactors orvessels under controlled pH, temperature, and mixing conditions. Oneskilled in the art would recognize that suitable processing time,temperature and pH conditions may vary depending on the type and amountof cellulosic material, polymeric acid catalyst, and solvent used. Thesefactors are described in further detail below.

Processing Time, Temperature and pH Conditions

In some embodiments, saccharification can last up to 200 hours. In otherembodiments, saccharification can take place from 1 to 96 hours, from 12to 72 hours, or from 12 to 48 hours.

In some embodiments, saccharification is performed at temperature in therange of about 25° C. to about 150° C. In other embodiments,saccharification is performed at temperature in the range of about 30°C. to about 125° C., or about 80° C. to about 120° C., or about 100° C.to 110° C.

The pH for saccharification is generally affected by the intrinsicproperties of the polymeric acid catalyst used. In particular, theacidic moiety of the polymeric acid catalyst may affect the pH ofsaccharification. For example, the use of sulfuric acid moiety in apolymeric acid catalyst results in saccharification at a pH of about 3.In other embodiments, saccharification is performed at a pH between 0and 6. The reacted effluent typically has a pH of at least 4, or a pHthat is compatible with other processes such as enzymatic treatment. Itshould be understood, however, that the pH can be modified andcontrolled by the addition of acids, bases or buffers.

Moreover, the pH may vary within the reactor. For example, high acidityat or near the surface of the catalyst may be observed, whereas regionsdistal to the catalyst surface may have a substantially neutral pH.Thus, one of skill would recognize that determination of the solution pHshould account for such spatial variation.

It should also be understood that, in certain embodiments, thesaccharification methods described herein may further include monitoringthe pH of the saccharification reaction, and optionally adjusting the pHwithin the reactor. In some instances, as a low pH in solution mayindicate an unstable polymeric acid catalyst, in which the catalyst maybe losing at least a portion of its acidic groups to the surroundingenvironment through leaching. In some embodiments, the pH near thesurface of the polymeric acid catalyst is below about 7, below about 6,or below about 5.

Amount of Cellulosic Material Used

The amount of the cellulosic material used in the methods describedherein relative to the amount solvent used may affect the rate ofreaction and yield. The amount of the cellulosic material used may becharacterized by the dry solids content. In certain embodiments, drysolids content refers to the total solids of a slurry as a percentage ona dry weight basis. In some embodiments, the dry solids content of thecellulosic materials is between about 5 wt % to about 95 wt %, betweenabout 10 wt % to about 80 wt %, between about 15 to about 75 wt %, orbetween about 15 to about 50 wt %.

Amount of Polymeric Acid Catalyst Used

The amount of the polymeric acid catalysts used in the saccharificationmethods described herein may depend on several factors including, forexample, the type of cellulosic material, the concentration of thecellulosic material, the type and number of pretreatment(s) applied tothe cellulosic material, and the reaction conditions (e.g., temperature,time, and pH). In one embodiment, the weight ratio of the polymeric acidcatalyst to the cellulose material is about 0.1 g/g to about 50 g/g,about 0.1 g/g to about 25 g/g, about 0.1 g/g to about 10 g/g, about 0.1g/g to about 5 g/g, about 0.1 g/g to about 2 g/g, about 0.1 g/g to about1 g/g, or about 0.1 to about 1.0 g/g.

Solvent

In certain embodiments, hydrolysis using the polymeric acid catalyst iscarried out in an aqueous environment. One suitable aqueous solvent iswater, which may be obtained from various sources. Generally, watersources with lower concentrations of ionic species are preferable, assuch ionic species may reduce effectiveness of the polymeric acidcatalyst. In some embodiments where the aqueous solvent is water, thewater has less than 10% of ionic species (e.g., salts of sodium,phosphorous, ammonium, magnesium, or other species found naturally inlignocellulosic biomass).

Moreover, as the cellulosic material is hydrolyzed, water is consumed ona mole-for-mole basis with the sugars produced. In certain embodiments,the saccharification methods described herein may further includemonitoring the amount of water present in the saccharification reactionand/or the ratio of water to biomass over a period of time. In otherembodiments, the saccharification methods described herein may furtherinclude supplying water directly to the reaction, for example, in theform of steam or steam condensate. For example, in some embodiments, thehydration conditions in the reactor is such that the water-to-cellulosicmaterial ratio is 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, or 1:5, orless than 1:5. It should be understood, however, that the ratio of waterto cellulosic material may be adjusted based on the specific polymericacid catalyst used.

Batch Versus Continuous Processing

Generally, the polymeric acid catalyst and the cellulosic materials areintroduced into an interior chamber of a reactor, either concurrently orsequentially. Saccharification can be performed in a batch process or acontinuous process. For example, in one embodiment, saccharification isperformed in a batch process, where the contents of the reactor arecontinuously mixed or blended, and all or a substantial amount of theproducts of the reaction are removed. In one variation, saccharificationis performed in a batch process, where the contents of the reactor areinitially intermingled or mixed but no further physical mixing isperformed. In another variation, saccharification is performed in abatch process, wherein once further mixing of the contents, or periodicmixing of the contents of the reactor, is performed (e.g., at one ormore times per hour), all or a substantial amount of the products of thereaction are removed after a certain period of time.

In other embodiments, saccharification is performed in a continuousprocess, where the contents flow through the reactor with an averagecontinuous flow rate but with no explicit mixing. After introduction ofthe polymeric acid catalyst and the cellulosic materials into thereactor, the contents of the reactor are continuously or periodicallymixed or blended, and after a period of time, less than all of theproducts of the reaction are removed. In one variation, saccharificationis performed in a continuous process, where the mixture containing thecatalyst and biomass is not actively mixed. Additionally, mixing ofcatalyst and biomass may occur as a result of the redistribution ofpolymeric acid catalysts settling by gravity, or the non-active mixingthat occurs as the material flows through a continuous reactor.

Reactors

The reactors used for the saccharification methods described herein maybe open or closed reactors suitable for use in containing the chemicalreactions described herein. Suitable reactors may include, for example,a fed-batch stirred reactor, a batch stirred reactor, a continuous flowstirred reactor with ultrafiltration, a continuous plug-flow columnreactor, an attrition reactor, or a reactor with intensive stirringinduced by an electromagnetic field. See e.g., Fernanda de CastilhosCorazza, Flavio Faria de Moraes, Gisella Maria Zanin and Ivo Neitzel,Optimal control in fed-batch reactor for the cellobiose hydrolysis, ActaScientiarum. Technology, 25: 33-38 (2003); Gusakov, A. V., and Sinitsyn,A. P., Kinetics of the enzymatic hydrolysis of cellulose: 1. Amathematical model for a batch reactor process, Enz. Microb. Technol.,7: 346-352 (1985); Ryu, S. K., and Lee, J. M., Bioconversion of wastecellulose by using an attrition bioreactor, Biotechnol. Bioeng. 25:53-65 (1983); Gusakov, A. V., Sinitsyn, A. P., Davydkin, I. Y.,Davydkin, V. Y., Protas, O. V., Enhancement of enzymatic cellulosehydrolysis using a novel type of bioreactor with intensive stirringinduced by electromagnetic field, Appl. Biochem. Biotechnol., 56:141-153 (1996). Other suitable reactor types may include, for example,fluidized bed, upflow blanket, immobilized, and extruder type reactorsfor hydrolysis and/or fermentation.

In certain embodiments where saccharification is performed as acontinuous process, the reactor may include a continuous mixer, such asa screw mixer. The reactors may be generally fabricated from materialsthat are capable of withstanding the physical and chemical forcesexerted during the processes described herein. In some embodiments, suchmaterials used for the reactor are capable of tolerating highconcentrations of strong liquid acids; however, in other embodiments,such materials may not be resistant to strong acids.

Further, the reactor typically contains an outlet means for removal ofcontents (e.g., a sugar-containing solution) from the reactor.Optionally, such outlet means is connected to a device capable ofprocessing the contents removed from the reactor. Alternatively, theremoved contents are stored. In some embodiments, the outlet means ofthe reactor is linked to a continuous incubator into which the reactedcontents are introduced. The reactor may be filled with biomass by atop-load feeder containing a hopper capable of holding biomass. Further,the outlet means provides for removal of residual biomass by, e.g., ascrew feeder, by gravity, or a low shear screw.

It should also be understood that additional cellulosic material and/orcatalyst may be added to the reactor, either at the same time or oneafter the other.

Rate and Yield of Saccharification

The use of the polymeric acid catalysts described herein can increasethe rate and/or yield of saccharification. The ability of the polymericacid catalyst to hydrolyze the cellulose and hemicellulose components ofbiomass to soluble sugars can be measured by determining the effectivefirst-order rate constant,

${{k_{1}( {{species}\mspace{14mu} i} )} = {- \frac{\ln ( {1 - x_{i}} )}{\Delta \; t}}},$

where Δt is the duration of the reaction and X_(i) is the extent ofreaction for species i (e.g., glucan, xylan, arabinan). In someembodiments, the polymeric acid catalysts described herein are capableof degrading biomass into one or more sugars at a first-order rateconstant of at least 0.001 per hour, at least 0.01 per hour, at least0.1 per hour, at least 0.2 per hour, at least 0.3 per hour, at least 0.4per hour, at least 0.5 per hour, or at least 0.6 per hour.

The hydrolysis yield of the cellulose and hemicellulose components ofbiomass to soluble sugars by the polymeric acid catalyst can be measuredby determining the degree of polymerization of the residual biomass. Thelower the degree of polymerization of the residual biomass, the greaterthe hydrolysis yield. In some embodiments, the polymeric acid catalystsdescribed herein are capable of converting biomass into one or moresugars and residual biomass, wherein the residual biomass has a degreeof polymerization of less than 300, less than 250, less than 200, lessthan 150, less than 100, less than 90, less than 80, less than 70, lessthan 60, or less than 50.

d) Separation and Purification of the Sugars

In some embodiments, the method for degrading cellulosic material usingthe polymeric acid catalysts described herein further includesrecovering the sugars that are produced from the hydrolysis of thecellulosic material. In another embodiment, the method for degradingcellulosic material using the polymeric catalyst described hereinfurther includes recovering the degraded or converted cellulosicmaterial.

The sugars, which are typically soluble, can be separated from theinsoluble residual cellulosic material using technology well known inthe art such as, for example, centrifugation, filtration, and gravitysettling.

Separation of the sugars may be performed in the hydrolysis reactor orin a separator vessel. In an exemplary embodiment, the method fordegrading cellulosic material is performed in a system with a hydrolysisreactor and a separator vessel. Reactor effluent containing themonosaccharides and/or oligosaccharides is transferred into a separatorvessel and is washed with a solvent (e.g., water), by adding the solventinto the separator vessel and then separating the solvent in acontinuous centrifuge. Alternatively, in another exemplary embodiment, areactor effluent containing residual solids (e.g., residual cellulosicmaterials) is removed from the reactor vessel and washed, for example,by conveying the solids on a porous base (e.g., a mesh belt) through asolvent (e.g., water) wash stream. Following contact of the stream withthe reacted solids, a liquid phase containing the monosaccharides and/oroligosaccharides is generated. Optionally, residual solids may beseparated by a cyclone. Suitable types of cyclones used for theseparation may include, for example, tangential cyclones, spark androtary separators, and axial and multi-cyclone units.

In another embodiment, separation of the sugars is performed by batch orcontinuous differential sedimentation. Reactor effluent is transferredto a separation vessel, optionally combined with water and/or enzymesfor further treatment of the effluent. Over a period of time, solidbiomaterials (e.g., residual treated biomass), the solid catalyst, andthe sugar-containing aqueous material can be separated by differentialsedimentation into a plurality of phases (or layers). Generally, thecatalyst layer may sediment to the bottom, and depending on the densityof the residual biomass, the biomass phase may be on top of, or below,the aqueous phase. When the phase separation is performed in a batchmode, the phases are sequentially removed, either from the top of thevessel or an outlet at the bottom of the vessel. When the phaseseparation is performed in a continuous mode, the separation vesselcontains one or more than one outlet means (e.g., two, three, four, ormore than four), generally located at different vertical planes on alateral wall of the separation vessel, such that one, two, or threephases are removed from the vessel. The removed phases are transferredto subsequent vessels or other storage means. By these processes, one ofskill in the art would be able to capture (1) the catalyst layer and theaqueous layer or biomass layer separately, or (2) the catalyst, aqueous,and biomass layers separately, allowing efficient catalyst recycling,retreatment of biomass, and separation of sugars. Moreover, controllingrate of phase removal and other parameters allows for increasedefficiency of catalyst recovery. Subsequent to removal of each of theseparated phases, the catalyst and/or biomass may be separately washedby the aqueous layer to remove adhered sugar molecules.

The sugars isolated from the vessel may be subjected to furtherprocessing steps (e.g., as drying, fermentation) to produce biofuels andother bio-products. In some embodiments, the monosaccharides that areisolated may be at least 1% pure, at least 5% pure, at least 10% pure,at least 20% pure, at least 40% pure, at least 60% pure, at least 80%pure, at least 90% pure, at least 95% pure, at least 99% pure, orgreater than 99% pure, as determined by analytical procedures known inthe art, such as determination by high performance liquid chromatography(HPLC), functionalization and analysis by gas chromatography, massspectrometry, spectrophotometric procedures based on chromophorecomplexation and/or carbohydrate oxidation-reduction chemistry.

The residual biomass isolated from the vessels may be useful as acombustion fuel or as a feed source of non-human animals such aslivestock.

Polymeric Acid Catalyst-Containing Compositions

Provided herein are also compositions involving the polymeric acidcatalysts that can be used in a variety of methods described herein,including the break-down of cellulosic material.

In one aspect, provided are compositions that include biomass, and thepolymeric acid catalysts described herein. In some embodiments, thecomposition further includes a solvent (e.g., water). In someembodiments, the biomass includes cellulose, hemicellulose, or acombination thereof.

In yet another aspect, provided are compositions that include thepolymeric acid catalysts described herein, one or more sugars, andresidual biomass. In some embodiments, the one or more sugars are one ormore monosaccharides, one or more oligosaccharides, or a mixturethereof. In certain embodiments, the one or more sugars are two or moresugars comprising at least one C4-C6 monosaccharide and at least oneoligosaccharide. In one embodiment, the one or more sugars are selectedfrom the group consisting of glucose, galactose, fructose, xylose, andarabinose.

Catalytic Intermediates

When the polymeric acid catalysts are used to degrade cellulosicmaterials, as described above, a catalytic intermediate is formed.Provided herein are also the catalytic intermediates, where thepolymeric acid catalyst coordinates with the cellulosic material. Thepolymeric acid catalyst may be hydrogen-bonded to the cellulose and/orhemicellulose to break down the cellulosic material to producemonosaccharides and oligosaccharides.

The ionic moiety of the polymeric acid catalysts can help to break downthe tertiary structure of the cellulosic materials. In some embodiments,the ionic moiety can disrupt inter- and intra-molecular hydrogen bondingin polysaccharide materials. Disruption of the hydrogen bonding of thetertiary structure can allow the acidic moiety to more readily accessthe glycosidic bonds of the polysaccharides. In other embodiments, theacidic moiety can disrupt the glycosidic bonds of the polysaccharides.Accordingly, the combination of the two functional moieties on a singlepolymer can provide for a catalyst that is effective in the break-downof polysaccharides using relatively mild conditions as compared to thosemethods that employ a more corrosive acid, or methods that employ harshconditions such as high temperatures or pressure.

In certain embodiments of the saccharification intermediate, the ionicmoiety of the polymer is hydrogen-bonded to the carbohydrate alcoholgroups present in cellulose, hemicellulose, and other oxygen-containingcomponents of biomass. In certain embodiments of the saccharificationintermediate, the acidic moiety of the polymer is hydrogen-bonded to thecarbohydrate alcohol groups present in cellulose, hemicellulose, andother oxygen-containing components of lignocellulosic biomass, includingthe glycosidic linkages between sugar monomers. Without wishing to bebound by any theory, in certain embodiments of the saccharificationintermediate, the hydrogen-bonds between an exemplary polymer and thecarbohydrate alcohol groups present in the biomass may be as depicted inFIG. 9.

Downstream Products

a) Fermentation of Isolated Sugars

The sugars obtained from hydrolysis of cellulosic material may be usedin downstream processes to produce biofuels and other bio-basedchemicals. In another aspect, the one or more sugars obtained fromhydrolysis of cellulosic material using the polymeric acid catalystdescribed herein may be fermented to produce one or more downstreamproducts (e.g., ethanol and other biofuels, vitamins, lipids, proteins).

In some embodiments, saccharification may be combined with fermentationin a separate or a simultaneous process. The fermentation may use theaqueous sugar phase or, if the sugars are not substantially purifiedfrom the reacted biomass, the fermentation may be performed on an impuremixture of sugars and reacted biomass. Such methods include, forexample, separate hydrolysis and fermentation (SHF), simultaneoussaccharification and fermentation (SSF), simultaneous saccharificationand cofermentation (SSCF), hybrid hydrolysis and fermentation (HHF),separate hydrolysis and co-fermentation (SHCF), hybrid hydrolysis andco-fermentation (HHCF), and direct microbial conversion (DMC).

For example, SHF uses separate process steps to first enzymaticallyhydrolyze cellulosic material to fermentable sugars (e.g., glucose,cellobiose, cellotriose, and pentose sugars), and then ferment thesugars to ethanol.

In SSF, the enzymatic hydrolysis of cellulosic material and thefermentation of sugars to ethanol are combined in one step. SeePhilippidis, G. P., Cellulose bioconversion technology, in Handbook onBioethanol: Production and Utilization, Wyman, C. E., ed., Taylor &Francis, Washington, D.C., 179-212 (1996).

SSCF involves the cofermentation of multiple sugars. See Sheehan, J.,and Himmel, M., Enzymes, energy and the environment: A strategicperspective on the U.S. Department of Energy's research and developmentactivities for bioethanol, Biotechnol. Prog., 15: 817-827 (1999).

HHF involves a separate hydrolysis step, and in addition a simultaneoussaccharification and hydrolysis step, which can be carried out in thesame reactor. The steps in an HHF process can be carried out atdifferent temperatures; for example, high temperature enzymaticsaccharification followed by SSF at a lower temperature that thefermentation strain can tolerate.

DMC combines all three processes (enzyme production, hydrolysis, andfermentation) in one or more steps where the same organism is used toproduce the enzymes for conversion of the cellulosic material tofermentable sugars and to convert the fermentable sugars into a finalproduct. See Lynd, L. R., Weimer, P. J., van Zyl, W. H., and Pretorius,I. S., Microbial cellulose utilization: Fundamentals and biotechnology,Microbiol. Mol. Biol. Reviews, 66: 506-577 (2002).

General Methods of Preparing the Polymeric Acid Catalysts

The polymers described herein can be made using polymerizationtechniques known in the art, including for example techniques toinitiate polymerization of a plurality of monomer units.

In some embodiments, the polymers described herein can be formed byfirst forming an intermediate polymer functionalized with the ionicgroup, but is free or substantially free of the acidic group. Theintermediate polymer can then be functionalized with the acidic group.

In other embodiments, the polymers described herein can be formed byfirst forming an intermediate polymer functionalized with the acidicgroup, but is free or substantially free of the ionic group. Theintermediate polymer can then be functionalized with the ionic group.

In yet other embodiments, the polymer described herein can be formed bypolymerizing monomers with both acidic and ionic groups.

Provided herein are also such intermediate polymers, including thoseobtained at different points within a synthetic pathway for producingthe fully functionalized polymers described herein. In some embodiments,the polymers described herein can be made, for example, on a scale of atleast 100 g, or at least 1 kg, in a batch or continuous process.

EXAMPLES Preparation of Polymeric Materials

Except where otherwise indicated, commercial reagents were obtained fromSigma-Aldrich, St. Louis, Mo., USA, and were purified prior to usefollowing the guidelines of Perrin and Armarego. See Perrin, D. D. &Armarego, W. L. F., Purification of Laboratory Chemicals, 3rd ed.;Pergamon Press, Oxford, 1988. Nitrogen gas for use in chemical reactionswas of ultra-pure grade, and was dried by passing it through a dryingtube containing phosphorous pentoxide. Unless indicated otherwise, allnon-aqueous reagents were transferred under an inert atmosphere viasyringe or Schlenk flask. Organic solutions were concentrated underreduced pressure on a Buchi rotary evaporator. Where necessary,chromatographic purification of reactants or products was accomplishedusing forced-flow chromatography on 60 mesh silica gel according to themethod described of Still et al., See Still et al., J. Org. Chem., 43:2923 (1978). Thin-layer chromatography (TLC) was performed usingsilica-coated glass plates. Visualization of the developed chromatogramwas performed using either Cerium Molybdate (i.e., Hanessian) stain orKMnO₄ stain, with gentle heating, as required. Fourier-TransformInfrared (FTIR) spectroscopic analysis of solid samples was performed ona Perkin-Elmer 1600 instrument equipped with a horizontal attenuatedtotal reflectance (ATR) attachment using a Zinc Selenide (ZnSe) crystal.

Example 1 Preparation ofpoly[styrene-co-vinylbenzylchloride-co-divinylbenzene]

To a 500 mL round bottom flask (RBF) containing a stirred solution of1.08 g of poly(vinylalcohol) in 250.0 mL of deionized H₂O at 0° C., wasgradually added a solution containing 50.04 g (327.9 mmol) ofvinylbenzyl chloride (mixture of 3- and 4-isomers), 10.13 g (97.3 mmol)of styrene, 1.08 g (8.306 mmol) of divinylbenzene (DVB, mixture of 3-and 4-isomers) and 1.507 g (9.2 mmol) of azobisisobutyronitrile (AIBN)in 150 mL of a 1:1 (by volume) mixture of benzene/tetrahydrofuran (THF)at 0° C. After 2 hours of stiffing at 0° C. to homogenize the mixture,the reaction flask was transferred to an oil bath to increase thereaction temperature to 75° C., and the mixture was stirred vigorouslyfor 28 hours. The resulting polymer beads were vacuum filtered using afritted-glass funnel to collect the polymer product. The beads werewashed repeatedly with 20% (by volume) methanol in water, THF, and MeOH,and dried overnight at 50° C. under reduced pressure to yield 59.84 g ofpolymer. The polymer beads were separated by size using sieves with meshsizes 100, 200, and 400.

Example 2 Preparation ofpoly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 50 g, 200 mmol) was charged into a 500 mL three neck flask (TNF)equipped with a mechanical stirrer, a dry nitrogen line, and purgevalve. Dry dimethylformamide (185 ml) was added into the flask (viacannula under N₂) and stirred to form a viscous slurry of polymer resin.1-Methylimidazole (36.5 g, 445 mmol) was then added and stirred at 95°C. for 8 h. After cooling, the reaction mixture was filtered using afritted glass funnel under vacuum, washed sequentially with de-ionizedwater and ethanol, and finally air dried.

The chemical functionalization of the polymer material, expressed inmillimoles of functional groups per gram of dry polymer resin (mmol/g)was determined by ion exchange titrimetry. For the determination ofcation-exchangable acidic protons, a known dry mass of polymer resin wasadded to a saturated aqueous solution of sodium chloride and titratedagainst a standard sodium hydroxide solution to the phenolphthalein endpoint. For the determination of anion-exchangeable ionic chloridecontent, a known dry mass of polymer resin was added to an aqueoussolution of sodium nitrate and neutralized with sodium carbonate. Theresulting mixture was titrated against a standardized solution of silvernitrate to the potassium chromate endpoint. For polymeric materials inwhich the exchangeable anion was not chloride, the polymer was firsttreated by stirring the material in aqueous hydrochloric acid, followedby washing repeatedly with water until the effluent was neutral (asdetermined by pH paper). The chemical functionalization of the polymerresin with methylimidazolium chloride groups was determined to be 2.60mmol/g via gravimetry and 2.61 mmol/g via titrimetry.

Example 3 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumbisulfate-co-divinylbenzene]

Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene](63 g) was charged into a 500 mL flask equipped with a magnetic stir barand condenser. Cold concentrated sulfuric acid (>98% w/w, H₂SO₄, 300 mL)was gradually added into the flask under stirring which resulted information of dark-red colored slurry of resin. The slurry was stirred at85° C. for 4 h. After cooling to room temperature, the reaction mixturewas filtered using fritted glass funnel under vacuum and then washedrepeatedly with de-ionized water until the effluent was neutral, asdetermined by pH paper. The sulfonated resin beads were finally washedwith ethanol and air dried. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 1.60mmol/g, as determined by titrimetry following the procedure of Example2.

Example 4 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumbisulfate-co-divinylbenzene] (sample of example 3), contained in frittedglass funnel, was washed repeatedly with 0.1 M HCl solution to ensurecomplete exchange of HSO₄ ⁻ with Cl⁻. The resin was then washed withde-ionized water until the effluent was neutral, as determined by pHpaper. The resin was finally air-dried.

Example 5 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumacetate-co-divinylbenzene]

The suspension of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumbisulfate-co-divinylbenzene] (sample of example 3) in 10% aqueous aceticacid solution was stirred for 2 h at 60° C. to ensure complete exchangeof HSO₄ ⁻ with AcO⁻. The resin was filtered using fritted glass funneland then washed multiple times with de-ionized water until the effluentwas neutral. The resin was finally air-dried.

Example 6 Preparation ofpoly[styrene-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 250 three neck flask (TNF)equipped with a mechanical stirrer, a dry nitrogen line, and purgevalve. Dry dimethylformamide (80 ml) was added into the flask (viacannula under N₂) and stirred to give viscous resin slurry.1-Ethylimidazole (4.3 g, 44.8 mmol) was then added to the resin slurryand stirred at 95° C. under 8 h. After cooling, the reaction mixture wasfiltered using fritted glass funnel under vacuum, washed sequentiallywith de-ionized water and ethanol, and finally air dried. The chemicalfunctionalization of the polymer resin with ethylimidazolium chloridegroups was determined to be 1.80 mmol/g, as determined by titrimetryfollowing the procedure of Example 1.

Example 7 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumbisulfate-co-divinylbenzene]

Poly[styrene-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene] (5 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 45 mL) was gradually added into theflask under stirring which resulted in the formation of dark-red coloreduniform slurry of resin. The slurry was stirred at 95-100° C. for 6 h.After cooling, the reaction mixture was filtered using fritted glassfunnel under vacuum and then washed repeatedly with de-ionized wateruntil the effluent was neutral, as determined by pH paper. Thesulfonated beads were finally washed with ethanol and air dried. Thechemical functionalization of the polymer with sulfonic acid groups wasdetermined to be 1.97 mmol/g, as determined by titrimetry following theprocedure of Example 2.

Example 8 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumbisulfate-co-divinylbenzene] resin beads (sample of example 7) containedin fritted glass funnel was washed multiple times with 0.1 M HClsolution to ensure complete exchange of HSO₄ ⁻ with Cl⁻. The resin wasthen washed with de-ionized water until the effluent was neutral, asdetermined by pH paper. The resin was finally washed with ethanol andair dried.

Example 9 Preparation ofpoly[styrene-co-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Chloroform (50 ml) was added into theflask and stirred to form slurry of resin. Imidazole (2.8 g, 41.13 mmol)was then added to the resin slurry and stirred at 40° C. for 18 h. Aftercompletion of reaction, the reaction mixture was filtered using frittedglass funnel under vacuum, washed sequentially with de-ionized water andethanol, and finally air dried. The chemical functionalization of thepolymer resin with imidazolium chloride groups was determined to be 2.7mmol/g, as determined by titrimetry following the procedure of Example2.

Example 10 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]

Poly[styrene-co-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene] (5 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 80 mL) was gradually added into theflask and stirred to form dark-red colored slurry of resin. The slurrywas stirred at 95° C. for 8 h. After cooling, the reaction mixture wasfiltered using fritted glass funnel under vacuum and then washedrepeatedly with de-ionized water until the effluent was neutral, asdetermined by pH paper. The sulfonated beads were finally washed withethanol and air dried. The chemical functionalization of the polymerresin with sulfonic acid groups was determined to be 1.26 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 11 Preparation ofpoly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 4 g, 16 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (50 ml) was addedinto the flask (via cannula under N₂) and stirred to form viscous slurryof polymer resin. 1-Methylbenzimidazole (3.2 g, 24.2 mmol) was thenadded to the resin slurry and the resulting reaction mixture was stirredat 95° C. for 18 h. After cooling, the reaction mixture was filteredusing fritted glass funnel under vacuum, washed sequentially withde-ionized water and ethanol, and finally air dried. The chemicalfunctionalization of the polymer with methylbenzimidazolium chloridegroups was determined to be 1.63 mmol/g, as determined by titrimetryfollowing the procedure of Example 2.

Example 12 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-iumbisulfate-co-divinylbenzene]

Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-benzoimidazol-1-iumchloride-co-divinylbenzene] (5.5 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 42 mL) and fuming sulfuric acid (20%free SO₃, 8 mL) was gradually added into the flask and stirred to formdark-red colored slurry of resin. The slurry was stirred at 85° C. for 4h. After cooling, the reaction mixture was filtered using fritted glassfunnel under vacuum and then washed repeatedly with de-ionized wateruntil the effluent was neutral, as determined by pH paper. Thesulfonated beads were finally washed with ethanol and air dried. Thechemical functionalization of the polymer with sulfonic acid groups wasdetermined to be 1.53 mmol/g, as determined by titrimetry following theprocedure of Example 2.

Example 13 Preparation of poly[styrene-co-1-(4-vinylbenzyl)-pyridiniumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 5 g, 20 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (45 ml) was addedinto the flask (via cannula under N₂) while stirring and consequently,the uniform viscous slurry of polymer resin was obtained. Pyridine (3mL, 37.17 mmol) was then added to the resin slurry and stirred at 85-90°C. for 18 h. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum, washed sequentially with de-ionizedwater and ethanol, and finally air dried. The chemical functionalizationof the polymer resin with pyridinium chloride groups was determined tobe 3.79 mmol/g, as determined by titrimetry following the procedure ofExample 2.

Example 14 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-divinylbenzene]

Poly[styrene-co-1-(4-vinylbenzyl)-pyridinium chloride-co-divinylbenzene](4 g) resin beads were charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Cold concentrated sulfuric acid (>98%w/w, H₂SO₄, 45 mL) was gradually added into the flask under stirringwhich consequently resulted in the formation of dark-red colored uniformslurry of resin. The slurry was heated at 95-100° C. under continuousstirring for 5 h. After completion of reaction, the cooled reactionmixture was filtered using fritted glass funnel under vacuum and thenwashed repeatedly with de-ionized water until the effluent was neutral,as determined by pH paper. The resin beads were finally washed withethanol and air dried. The chemical functionalization of the polymerwith sulfonic acid groups was determined to be 0.64 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 15 Preparation of poly[styrene-co-1-(4-vinylbenzyl)-pyridiniumchloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (80 ml) was addedinto the flask (via cannula under N₂) while stirring which resulted inthe formation of viscous slurry of polymer resin. Pyridine (1.6 mL,19.82 mmol) and 1-methylimidazole (1.7 mL, 21.62 mmol) were then addedto the resin slurry and the resulting reaction mixture was stirred at95° C. for 18 h. After completion of reaction, the reaction mixture wascooled, filtered using fritted glass funnel under vacuum, washedsequentially with de-ionized water and ethanol, and finally air dried.The chemical functionalization of the polymer with pyridinium chlorideand 1-methylimidazolium chloride groups was determined to be 3.79mmol/g, as determined by titrimetry following the procedure of Example2.

Example 16 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-1-(4-vinylbenzyl)-pyridiniumchloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumbisulfate-co-divinylbenzene]

Poly[styrene-co-1-(4-vinylbenzyl)-pyridiniumchloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene] (5 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 75 mL) and fuming sulfuric acid (20%free SO₃, 2 mL) were then gradually added into the flask under stirringwhich consequently resulted in the formation of dark-red colored uniformslurry of resin. The slurry was heated at 95-100° C. under continuousstirring for 12 h. After completion of reaction, the cooled reactionmixture was filtered using fritted glass funnel under vacuum and thenwashed repeatedly with de-ionized water until the effluent was neutral,as determined by pH paper. The sulfonated resin beads were finallywashed with ethanol and air dried. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 1.16mmol/g, as determined by titrimetry following the procedure of Example2.

Example 17 Preparation ofpoly[styrene-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (85 ml) was addedinto the flask (via cannula under N₂) while stirring which resulted inthe formation of uniform viscous slurry of polymer resin.1-Methylmorpholine (5.4 mL, 49.12 mmol) were then added to the resinslurry and the resulting reaction mixture was stirred at 95° C. for 18h. After cooling, the reaction mixture was filtered using fritted glassfunnel under vacuum, washed sequentially with de-ionized water andethanol, and finally air dried. The chemical functionalization of thepolymer with methylmorpholinium chloride groups was determined to be3.33 mmol/g, as determined by titrimetry following the procedure ofExample 2.

Example 18 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-iumbisulfate-co-divinylbenzene]

Poly[styrene-co-1-4-methyl-4-(4-vinylbenzyl)-morpholin-4-iumchloride-co-divinylbenzene] (8 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 50 mL) was gradually added into theflask under stirring which consequently resulted in the formation ofdark-red colored slurry. The slurry was stirred at 90° C. for 8 h. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum, washed repeatedly with de-ionized water until the effluentwas neutral, as determined by pH paper. The sulfonated resin beads werefinally washed with ethanol and air dried. The chemicalfunctionalization of the polymer with sulfonic acid groups wasdetermined to be 1.18 mmol/g, as determined by titrimetry following theprocedure of Example 2.

Example 19 Preparation of[polystyrene-co-triphenyl-(4-vinylbenzyl)-phosphoniumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (80 ml) was addedinto the flask (via cannula under N₂) while stirring and the uniformviscous slurry of polymer resin was obtained. Triphenylphosphine (11.6g, 44.23 mmol) was then added to the resin slurry and the resultingreaction mixture was stirred at 95° C. for 18 h. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with de-ionized water and ethanol, and finally airdried. The chemical functionalization of the polymer withtriphenylphosphonium chloride groups was determined to be 2.07 mmol/g,as determined by titrimetry following the procedure of Example 2.

Example 20 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-triphenyl-(4-vinylbenzyl)-phosphoniumbisulfate-co-divinylbenzene]

Poly(styrene-co-triphenyl-(4-vinylbenzyl)-phosphoniumchloride-co-divinylbenzene) (7 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 40 mL) and fuming sulfuric acid (20%free SO₃, 15 mL) were gradually added into the flask under stirringwhich consequently resulted in the formation of dark-red colored slurry.The slurry was stirred at 95° C. for 8 h. After cooling, the reactionmixture was filtered using fritted glass funnel under vacuum, washedrepeatedly with de-ionized water until the effluent was neutral, asdetermined by pH paper. The sulfonated resin beads were finally washedwith ethanol and air dried. The chemical functionalization of thepolymer with sulfonic acid groups was determined to be 2.12 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 21 Preparation ofpoly[styrene-co-1-(4-vinylbenzyl)-piperidine-co-divinylbenzene]

Poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) (Cl⁻density=˜4.0 mmol/g, 10 g, 40 mmol) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Dry dimethylformamide(50 ml) was added into the flask (via cannula under N₂) while stirringwhich resulted in the formation of uniform viscous slurry of polymerresin. Piperidine (4 g, 46.98 mmol) was then added to the resin slurryand the resulting reaction mixture was stirred at 95° C. for 16 h. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum, washed sequentially with de-ionized water and ethanol, andfinally air dried.

Example 22 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-1-(4-vinylbenzyl)-piperidine-co-divinyl benzene]

Poly[styrene-co-1-(4-vinylbenzyl)-piperidine-co-divinyl benzene] (7 g)was charged into a 100 mL flask equipped with a magnetic stir bar andcondenser. Cold concentrated sulfuric acid (>98% w/w, H₂SO₄, 45 mL) andfuming sulfuric acid (20% free SO₃, 12 mL) were gradually added into theflask under stiffing which consequently resulted in the formation ofdark-red colored slurry. The slurry was stirred at 95° C. for 8 h. Aftercompletion of reaction, the cooled reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The resin beads were finally washed with ethanol and air dried.The chemical functionalization of the polymer with sulfonic acid groupswas determined to be 0.72 mmol/g, as determined by titrimetry followingthe procedure of Example 2.

Example 23 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium chloride-co-divinylbenzene]

Poly(styrene-co-4-(1-piperidino)methylstyrene-co-divinylbenzene) (4 g)was charged into a 100 mL flask equipped with a magnetic stir bar andcondenser. Dry dimethylformamide (40 ml) was added into the flask (viacannula under N₂) under stirring to obtain uniform viscous slurry.Iodomethane (1.2 ml) and potassium iodide (10 mg) were then added intothe flask. The reaction mixture was stirred at 95° C. for 24 h. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed multiple times with dilute HCl solution toensure complete exchange of I⁻ with Cl⁻. The resin was finally washedwith de-ionized water until the effluent was neutral, as determined bypH paper. The resin was finally air-dried.

Example 24 Preparation ofpoly[styrene-co-4-(4-vinylbenzyl)-morpholine-co-divinyl benzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (50 ml) was addedinto the flask (via cannula under N₂) while stirring and consequently,the uniform viscous slurry of polymer resin was obtained. Morpholine (4g, 45.92 mmol) was then added to the resin slurry and the resultingreaction mixture was heated at 95° C. under continuous stiffing for 16h. After completion of reaction, the reaction mixture was cooled,filtered using fritted glass funnel under vacuum, washed sequentiallywith de-ionized water and ethanol, and finally air dried.

Example 25 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-4-(4-vinylbenzyl)-morpholine-co-divinyl benzene]

Poly[styrene-co-4-(4-vinylbenzyl)-morpholine-co-divinyl benzene] (10 g)was charged into a 200 mL flask equipped with a magnetic stir bar andcondenser. Cold concentrated sulfuric acid (>98% w/w, H₂SO₄, 90 mL) andfuming sulfuric acid (20% free SO₃, 10 mL) were gradually added into theflask while stirring which consequently resulted in the formation ofdark-red colored slurry. The slurry was stirred at 95° C. for 8 h. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed repeatedly with de-ionized water until theeffluent was neutral, as determined by pH paper. The sulfonated resinbeads were finally washed with ethanol and air dried. The chemicalfunctionalization of the polymer with sulfonic acid groups wasdetermined to be 0.34 mmol/g, as determined by titrimetry following theprocedure of Example 2.

Example 26 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene]

Poly[styrene-co-4-vinylbenzenesulfonicacid-co-4-(4-vinylbenzyl)-morpholine-co-divinyl benzene] (6 g) wascharged into a 100 mL flask equipped with a magnetic stir bar andcondenser. Methanol (60 mL) was then charged into the flask, followed byaddition of hydrogen peroxide (30% solution in water, 8.5 mL). Thereaction mixture was refluxed under continuous stirring for 8 h. Aftercooling, the reaction mixture was filtered, washed sequentially withde-ionized water and ethanol, and finally air dried.

Example 27 Preparation of poly[styrene-co-4-vinylbenzyl-triethylammoniumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (80 ml) was addedinto the flask (via cannula under N₂) while stirring and consequentlythe uniform viscous slurry of polymer resin was obtained. Triethylamine(5 mL, 49.41 mmol) was then added to the resin slurry and the resultingreaction mixture was stirred at 95° C. for 18 h. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with de-ionized water and ethanol, and finally airdried. The chemical functionalization of the polymer resin withtriethylammonium chloride groups was determined to be 2.61 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 28 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-triethyl-(4-vinylbenzyl)-ammonium chloride-co-divinylbenzene]

Poly[styrene-co-triethyl-(4-vinylbenzyl)-ammoniumchloride-co-divinylbenzene] (6 g) was charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Cold concentratedsulfuric acid (>98% w/w, H₂SO₄, 60 mL) was gradually added into theflask under stirring which consequently resulted in the formation ofdark-red colored uniform slurry of resin. The slurry was stirred at95-100° C. for 8 h. After cooling, the reaction mixture was filteredusing fritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated resin beads were finally washed with ethanol andair dried. The chemical functionalization of the polymer with sulfonicacid groups was determined to be 0.31 mmol/g, as determined bytitrimetry following the procedure of Example 2.

Example 29 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-vinylbenzylchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) (6 g) wascharged into a 100 mL flask equipped with a magnetic stir bar andcondenser. Fuming sulfuric acid (20% free SO₃, 25 mL) was graduallyadded into the flask under stirring which consequently resulted in theformation of dark-red colored slurry. The slurry was stirred at 90° C.for 5 h. After cooling, the reaction mixture was filtered using frittedglass funnel under vacuum, washed sequentially with de-ionized water andethanol, and finally air dried. The chemical functionalization of thepolymer with sulfonic acid groups was determined to be 0.34 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 30 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly[styrene-co-4-vinylbenzenesulfonicacid-co-vinylbenzylchloride-co-divinylbenzene] (5 g) was charged into a100 mL flask equipped with a magnetic stir bar and condenser. Drydimethylformamide (20 ml) was added into the flask (via cannula underN₂) while stirring and the uniform viscous slurry of polymer resin wasobtained. 1-Methylimidazole (3 mL, 49.41 mmol) was then added to theresin slurry and the resulting reaction mixture was stirred at 95° C.for 18 h. After cooling, reaction mixture was filtered using frittedglass funnel under vacuum and then washed repeatedly with de-ionizedwater. The resin beads were finally washed with ethanol and air dried.The chemical functionalization of the polymer with sulfonic acid groupand methylimidiazolium chloride groups was determined to be 0.23 mmol/gand 2.63 mmol/g, respectively, as determined by titrimetry following theprocedure of Example 2.

Example 31 Preparation ofpoly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-4-boronyl-1-(4-vinylbenzyl)-pyridiniumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (80 ml) was addedinto the flask (via cannula under N₂) while stirring and consequentlythe uniform viscous slurry of polymer resin was obtained.4-Pyridyl-boronic acid (1.8 g, 14.6 mmol) was then added to the resinslurry and the resulting reaction mixture was stirred at 95° C. for 2days. 1-Methylimidazole (3 mL, 49.41 mmol) was then added to thereaction mixture and stirred further at 95° C. for 1 day. After coolingto room temperature, the reaction mixture was filtered using frittedglass funnel under vacuum, washed sequentially with de-ionized water andethanol, and finally air dried. The chemical functionalization of thepolymer with boronic acid group was determined to be 0.28 mmol/grespectively, as determined by titrimetry following the procedure ofExample 2.

Example 32 Preparation ofpoly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]

Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene] (Cl⁻ density=˜2.73 mmol/g, 5 g) was chargedinto a 100 mL flask equipped with a magnetic stir bar and condenser.Triethylphosphite (70 ml) was added into the flask and the resultingsuspension was stirred at 120° C. for 2 days. The reaction mixture wasfiltered using fritted glass funnel and the resin beads were washedrepeatedly with de-ionized water and ethanol. These resin beads werethen suspended in concentrated HCl (80 ml) and refluxed at 115° C. undercontinuous stirring for 24 h. After cooling to room temperature, thereaction mixture was filtered using fritted glass funnel under vacuumand then washed repeatedly with de-ionized water. The resin beads werefinally washed with ethanol and air dried. The chemicalfunctionalization of the polymer with phosphonic acid group andmethylimidiazolium chloride groups was determined to be 0.11 mmol/g and2.81 mmol/g, respectively, as determined by titrimetry following theprocedure of Example 2.

Example 33 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-vinylbenzylchloride-co-vinyl-2-pyridine-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-vinyl-2-pyridine-co-divinylbenzene)(5 g) was charged into a 100 mL flask equipped with a magnetic stir barand condenser. Cold concentrated sulfuric acid (>98% w/w, H₂SO₄, 80 mL)was gradually added into the flask under stirring which consequentlyresulted in the formation of dark-red colored slurry. The slurry wasstirred at 95° C. for 8 h. After cooling to room temperature, thereaction mixture was filtered using fritted glass funnel under vacuum,washed repeatedly with de-ionized water until the effluent was neutral,as determined by pH paper. The sulfonated beads were finally washed withethanol and air dried. The chemical functionalization of the polymerwith sulfonic acid groups was determined to be 3.49 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 34 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridiniumchloride-co-divinylbenzene]

Poly[styrene-co-4-vinylbenzenesulfonicacid-co-vinylbenzylchloride-co-vinyl-2-pyridine-co-divinylbenzene] (4 g)was charged into a 100 mL flask equipped with a magnetic stir bar andcondenser. Dry dimethylformamide (80 ml) was added into the flask (viacannula under N₂) under stiffing to obtain uniform viscous slurry.Iodomethane (1.9 ml) was then gradually added into the flask followed byaddition of potassium iodide (10 mg). The reaction mixture was stirredat 95° C. for 24 h. After cooling to room temperature, the cooledreaction mixture was filtered using fritted glass funnel under vacuumand then washed multiple times with dilute HCl solution to ensurecomplete exchange of I⁻ with Cl⁻. The resin beads were finally washedwith de-ionized water until the effluent was neutral, as determined bypH paper and then air-dried.

Example 35 Preparation of poly[styrene-co-4-vinylbenzenesulfonicacid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene]

Poly[styrene-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinyl benzene](3 g) was charged into a 100 mL flask equipped with a magnetic stir barand condenser. Cold concentrated sulfuric acid (>98% w/w, H₂SO₄, 45 mL)was gradually added into the flask under stirring which consequentlyresulted in the formation of dark-red colored slurry. The slurry wasstirred at 95° C. for 8 h. After cooling to room temperature, thereaction mixture was filtered using fritted glass funnel under vacuum,washed repeatedly with de-ionized water until the effluent was neutral,as determined by pH paper. The sulfonated beads were finally washed withethanol and air dried.

Example 36 Preparation of poly[styrene-co-4-vinylphenylphosphonicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene](Cl⁻ density=˜2.73 mmol/g, 5 g) was charged into a 100 mL flask equippedwith a magnetic stir bar and condenser. Diethylphosphite (30 ml) andt-butylperoxide (3.2 ml) were added into the flask and the resultingsuspension was stirred at 120° C. for 2 days. The reaction mixture wasfiltered using fritted glass funnel and the resin beads were washedrepeatedly with de-ionized water and ethanol. These resin beads werethen suspended in concentrated HCl (80 ml) and refluxed at 115° C. undercontinuous stirring for 2 days. After cooling to room temperature, thereaction mixture was filtered using fritted glass funnel under vacuumand then washed repeatedly with de-ionized water. The resin beads werefinally washed with ethanol and air dried. The chemicalfunctionalization of the polymer with aromatic phosphonic acid group wasdetermined to be 0.15 mmol/g, as determined by titrimetry following theprocedure of Example 2.

Example 37 Preparation ofpoly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dimethylformamide (50 ml) was addedinto the flask and stirred to form a slurry of resin. Imidazole (2.8 g,41.13 mmol) was then added to the resin slurry and stirred at 80° C. for8 h. The reaction mixture was then cooled to 40° C. and t-butoxide (1.8g) was added into the reaction mixture and stirred for 1 h.Bromoethylacetate (4 ml) was then added to and the reaction mixture wasstirred at 80° C. for 6 h. After cooling to room temperature, thereaction mixture was filtered using fritted glass funnel under vacuumand then washed repeatedly with de-ionized water. The washed resin beadswere suspended in the ethanolic sodium hydroxide solution and refluxedovernight. The resin beads were filtered and successively washed withdeionized water multiple times and ethanol, and finally air dried. Thechemical functionalization of the polymer with carboxylic acid group wasdetermined to be 0.09 mmol/g, as determined by titrimetry following theprocedure of Example 2.

Example 38 Preparation ofpoly[styrene-co-5-(4-vinylbenzylamino)-isophthalicacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (80 ml) was addedinto the flask (via cannula under N₂) while stirring and consequentlythe uniform viscous slurry of polymer resin was obtained. Dimethylaminoisophthalate (3.0 g, 14.3 mmol) was then added to the resin slurryand the resulting reaction mixture was stirred at 95° C. for 16 h.1-Methylimidazole (2.3 mL, 28.4 mmol) was then added to the reactionmixture and stirred further at 95° C. for 1 day. After cooling to roomtemperature, the reaction mixture was filtered using fritted glassfunnel under vacuum, washed sequentially with de-ionized water andethanol. The washed resin beads were suspended in the ethanolic sodiumhydroxide solution and refluxed overnight. The resin beads were filteredand successively washed with deionized water multiple times and ethanol,and finally air dried. The chemical functionalization of the polymerwith carboxylic acid group was determined to be 0.16 mmol/g, asdetermined by titrimetry following the procedure of Example 2.

Example 39 Preparation of poly[styrene-co-(4-vinylbenzylamino)-aceticacid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene]

Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (Cl⁻ density=˜4.0mmol/g, 10 g, 40 mmol) was charged into a 100 mL flask equipped with amagnetic stir bar and condenser. Dry dimethylformamide (80 ml) was addedinto the flask (via cannula under N₂) while stiffing and consequentlythe uniform viscous slurry of polymer resin was obtained. Glycine (1.2g, 15.9 mmol) was then added to the resin slurry and the resultingreaction mixture was stirred at 95° C. for 2 days. 1-Methylimidazole(2.3 mL, 28.4 mmol) was then added to the reaction mixture and stirredfurther at 95° C. for 12 hours. After cooling to room temperature, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with de-ionized water and ethanol, and finally airdried. The chemical functionalization of the polymer with carboxylicacid group was determined to be 0.05 mmol/g, as determined by titrimetryfollowing the procedure of Example 2.

Example 40 Preparation ofpoly[styrene-co-(1-vinyl-1H-imidazole)-co-divinylbenzene]

To a 500 mL round bottom flask (RBF) containing a stirred solution of1.00 g of poly(vinylalcohol) in 250.0 mL of deionized H₂O at 0° C. isgradually added a solution containing 35 g (371 mmol) of1-vinylimidazole, 10 g (96 mmol) of styrene, 1 g (7.7 mmol) ofdivinylbenzene (DVB) and 1.5 g (9.1 mmol) of azobisisobutyronitrile(AIBN) in 150 mL of a 1:1 (by volume) mixture of benzene/tetrahydrofuran(THF) at 0° C. After 2 hours of stirring at 0° C. to homogenize themixture, the reaction flask is transferred to an oil bath to increasethe reaction temperature to 75° C., and the mixture is stirredvigorously for 24 hours. The resulting polymer is vacuum filtered usinga fritted-glass funnel, washed repeatedly with 20% (by volume) methanolin water, THF, and MeOH, and then dried overnight at 50° C. underreduced pressure.

Example 41 Preparation of poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-vinylbenzylmethylmorpholiniumchloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)

1-methylimidazole (4.61 g, 56.2 mmol), 4-methylmorpholine (5.65 g, 56.2mmol), and triphenylphosphine (14.65, 55.9 mmol) were charged into a 500mL flask equipped with a magnetic stir bar and a condenser. Acetone (100ml) was added into the flask and mixture was stirred at 50° C. for 10min. Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (1% DVB, Cl⁻density=4.18 mmol/g dry resin, 40.22 g, 168 mmol) was charged into theflask while stirring until a uniform polymer suspension was obtained.The resulting reaction mixture was refluxed for 24 h. After cooling, thereaction mixture was filtered using a flitted glass funnel under vacuum,washed sequentially with acetone and ethyl acetate, and dried overnightat 70° C. The chemical functionalization of the polymer resin withchloride groups was determined to be 2.61 mmol/g dry resin viatitrimetry.

Example 42 Preparation of sulfonatedpoly(styrene-co-vinylbenzylmethylimidazoliumbisulfate-co-vinylbenzylmethylmorpholiniumbisulfate-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-vinylbenzylmethylmorpholiniumchloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)(35.02 g) was charged into a 500 mL flask equipped with a magnetic stirbar and condenser. Fuming sulfuric acid (20% free SO₃, 175 mL) wasgradually added into the flask and stirred to form dark-red resinsuspension. The mixture was stirred overnight at 90° C. After cooling toroom temperature, the reaction mixture was filtered using fritted glassfunnel under vacuum and then washed repeatedly with de-ionized wateruntil the effluent was neutral, as determined by pH paper. Thesulfonated polymer resin was air dried to a final moisture content of56% g H₂O/g wet polymer. The chemical functionalization of the polymerresin with sulfonic acid groups was determined to be 3.65 mmol/g dryresin.

Example 43 Preparation of poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-vinylbenzylmethylmorpholiniumchloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)

1-methylimidazole (7.02 g, 85.5 mmol), 4-methylmorpholine (4.37 g, 43.2mmol) and triphenylphosphine (11.09, 42.3 mmol) were charged into a 500mL flask equipped with a magnetic stir bar and condenser. Acetone (100ml) was added into the flask and mixture was stirred at 50° C. for 10min. Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (1% DVB, Cl⁻density=4.18 mmol/g dry resin, 40.38 g, 169 mmol) was charged into flaskwhile stirring until a uniform suspension was obtained. The resultingreaction mixture was refluxed for 18 h. After cooling, the reactionmixture was filtered using fritted glass funnel under vacuum, washedsequentially with acetone and ethyl acetate, and dried at 70° C.overnight. The chemical functionalization of the polymer resin withchloride groups was determined to be 2.36 mmol/g dry resin dry resin viatitrimetry.

Example 44 Preparation of sulfonatedpoly(styrene-co-vinylbenzylmethylimidazoliumbisulfate-co-vinylbenzylmethylmorpholiniumbisulfate-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-vinylbenzylmethylmorpholiniumchloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)(35.12 g) was charged into a 500 mL flask equipped with a magnetic stirbar and condenser. Fuming sulfuric acid (20% free SO₃, 175 mL) wasgradually added into the flask and stirred to form dark-red coloredslurry of resin. The slurry was stirred at 90° C. overnight. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed repeatedly with de-ionized water until theeffluent was neutral, as determined by pH paper. The sulfonated beadswere finally air dried. The chemical functionalization of the polymerresin with sulfonic acid groups was determined to be 4.38 mmol/g dryresin.

Example 45 Preparation of poly(styrene-co-vinylbenzylmethylmorpholiniumchloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)

4-methylmorpholine (8.65 g, 85.5 mmol) and triphenylphosphine (22.41,85.3 mmol) were charged into a 500 mL flask equipped with a magneticstir bar and condenser. Acetone (100 ml) was added into the flask andmixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (1% DVB, Cl⁻density=4.18 mmol/g dry resin, 40.12 g, 167 mmol) was charged into flaskwhile stirring until a uniform suspension was obtained. The resultingreaction mixture was refluxed for 24 h. After cooling, the reactionmixture was filtered using fritted glass funnel under vacuum, washedsequentially with acetone and ethyl acetate, and dried at 70° C.overnight. The chemical functionalization of the polymer resin withchloride groups was determined to be 2.22 mmol/g dry resin viatitrimetry.

Example 46 Preparation of sulfonatedpoly(styrene-co-vinylbenzylmethylmorpholiniumbisulfate-co-vinylbenzyltriphenylphosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-vinylbenzylmethylmorpholiniumchloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)(35.08 g) was charged into a 500 mL flask equipped with a magnetic stirbar and condenser. Fuming sulfuric acid (20% free SO₃, 175 mL) wasgradually added into the flask and stirred to form dark-red coloredslurry of resin. The slurry was stirred at 90° C. overnight. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed repeatedly with de-ionized water until theeffluent was neutral, as determined by pH paper. The sulfonated beadswere dried under air to a final moisture content of 52% g H₂O/g wetresin. The chemical functionalization of the polymer resin with sulfonicacid groups was determined to be 4.24 mmol/g dry resin.

Example 47 Preparation of Phenol-Formaldehyde Resin

Phenol (12.87 g, 136.8 mmol) was dispensed into a 100 mL round bottomflask (RBF) equipped with a stir bar and condenser. De-ionized water(10g) was charged into the flask. 37% Formalin solution (9.24 g, 110mmol) and oxalic acid (75 mg) were added. The resulting reaction mixturewas refluxed for 30 min. Additional oxalic acid (75 mg) was then addedand refluxing was continued for another 1 hour. Chunk of solid resin wasformed, which was ground to a coarse powder using a mortar and pestle.The resin was repeatedly washed with water and methanol and then driedat 70° C. overnight.

Example 48 Preparation of Chloromethylated Phenol-Formaldehyde Resin

Phenol-formaldehyde resin (5.23 g, 44 mmol) was dispensed into a 100 mLthree neck round bottom flask (RBF) equipped with a stir bar, condenserand nitrogen line. Anhydrous dichloroethane (DCE, 20 ml) was thencharged into the flask. To ice-cooled suspension of resin in DCE, zincchloride (6.83 g, 50 mmol) was added. Chloromethyl methyl ether (4.0 ml,51 mmol) was then added dropwise into the reaction. The mixture waswarmed to room temperature and stirred at 50° C. for 6 h. The productresin was recovered by vacuum filtration and washed sequentially withwater, acetone and dichloromethane. The washed resin was dried at 40° C.overnight.

Example 49 Preparation of Triphenylphosphine FunctionalizedPhenol-Formaldehyde Resin

Triphenylphosphine (10.12, 38.61 mmol) were charged into a 100 mL flaskequipped with a magnetic stir bar and condenser. Acetone (30 ml) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Chloromethylated phenol-formaldehyde resin (4.61 g, 38.03 mmol) wascharged into flask while stirring. The resulting reaction mixture wasrefluxed for 24 h. After cooling, the reaction mixture was filteredusing fritted glass funnel under vacuum, washed sequentially withacetone and ethyl acetate, and dried at 70° C. overnight.

Example 50 Preparation of Sulfonated Triphenylphosphine-FunctionalizedPhenol-Formaldehyde Resin

Triphenylphosphine-functionalized phenol-formaldehyde resin (5.12 g,13.4 mmol) was charged into a 100 mL flask equipped with a magnetic stirbar and condenser. Fuming sulfuric acid (20% free SO₃, 25 mL) wasgradually added into the flask and stirred to form dark-red coloredslurry of resin. The slurry was stirred at 90° C. overnight. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed repeatedly with de-ionized water until theeffluent was neutral, as determined by pH paper. The sulfonated resinwas dried under air to a final moisture content of 49% g H₂O/g wetresin. The chemical functionalization of the polymer resin with sulfonicacid groups was determined to be 3.85 mmol/g dry resin.

Example 51 Preparation ofpoly(styrene-co-vinylimidazole-co-divinylbenzene)

De-ionized water (75 mL) was charged into flask into a 500 mL three neckround bottom flask equipped with a mechanical stirrer, condenser and N₂line. Sodium chloride (1.18 g) and carboxymethylcellulose (0.61 g) werecharged into the flask and stirred for 5 min. The solution ofvinylimidazole (3.9 mL, 42.62 mmol), styrene (4.9 mL, 42.33 mmol) anddivinylbenzene (0.9 mL, 4.0 mmol) in iso-octanol (25 mL) was chargedinto flask. The resulting emulsion was stirred at 500 rpm at roomtemperature for 1 h. Benzoyl peroxide (75%, 1.205 g) was added, andtemperature was raised to 80° C. The reaction mixture was heated for 8 hat 80° C. with stiffing rate of 500 rpm. The polymer product wasrecovered by vacuum filtration and washed with water and acetonemultiple times. The isolated polymer was purified by soxhlet extractionwith water and acetone. The resin was dried at 40° C. overnight.

Example 52 Preparation of poly(styrene-co-vinylmethylimidazoliumiodide-co-divinylbenzene)

Poly(styrene-co-vinylimidazole-co-divinylbenzene) (3.49 g, 39 mmol) wasdispensed into a 100 mL three neck round bottom flask (RBF) equippedwith a stir bar, condenser and nitrogen line. Anhydrous tetrahydrofuran(20 ml) was then charged into the flask. To ice-cooled suspension ofresin in tetrahydrofuran, potassium t-butoxide (5.62 g, 50 mmol) wasadded and stirred for 30 min. Iodomethane (3.2 ml, 51 mmol) was thenadded dropwise into the reaction. The mixture was warmed to roomtemperature and stirred at 50° C. for 6 h. The product resin wasrecovered by vacuum filtration and washed sequentially with water,acetone and dichloromethane. The washed resin was dried at 40° C.overnight.

Example 53 Preparation of sulfonatedpoly(styrene-co-vinylmethylimidazolium bisulfate-co-divinylbenzene)

Poly(styrene-co-vinylmethylimidazolium iodide-co-divinylbenzene) (3.89g, 27.8 mmol) was charged into a 100 mL flask equipped with a magneticstir bar and condenser. Fuming sulfuric acid (20% free SO₃, 20 mL) wasgradually added into the flask and stirred to form dark-red coloredslurry. The slurry was stirred at 90° C. overnight. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuumand then washed repeatedly with de-ionized water until the effluent wasneutral, as determined by pH paper. The sulfonated polymer was driedunder air to a final moisture content of 51% g H₂O/g wet resin.

Example 54 Preparation ofpoly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene)

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged triphenylphosphine (38.44 g, 145.1 mmol). Acetone (50 mL) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (8% DVB, Cl⁻density=4.0 mmol/g dry resin, 30.12 g, 115.6 mmol) was charged intoflask while stirring until a uniform suspension was obtained. Theresulting reaction mixture was refluxed for 24 h. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with acetone and ethyl acetate, and dried at 70° C.overnight. The chemical functionalization of the polymer resin withtriphenylphosphonium chloride groups was determined to be 1.94 mmol/gdry resin via titrimetry.

Example 55 Preparation of sulfonatedpoly(styrene-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene) (40.12 g) was charged into a 500 mL flaskequipped with a magnetic stir bar and condenser. Fuming sulfuric acid(20% free SO₃, 160 mL) was gradually added into the flask and stirred toform dark-red colored slurry of resin. The slurry was stirred at 90° C.overnight. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated beads were dried under air to a final moisturecontent of 54% g H₂O/g wet resin. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 4.39 mmol/gdry resin.

Example 56 Preparation ofpoly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged triphenylphosphine (50.22 g, 189.6 mmol). Acetone (50 mL) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (4% DVB, Cl⁻density=5.2 mmol/g dry resin, 30.06 g, 152.08 mmol) was charged intoflask while stirring until a uniform suspension was obtained. Theresulting reaction mixture was refluxed for 24 h. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with acetone and ethyl acetate, and dried at 70° C.overnight. The chemical functionalization of the polymer resin withtriphenylphosphonium chloride groups was determined to be 2.00 mmol/gdry resin via titrimetry.

Example 57 Preparation of sulfonatedpoly(styrene-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene) (40.04 g,) was charged into a 500 mL flaskequipped with a magnetic stir bar and condenser. Fuming sulfuric acid(20% free SO₃, 160 mL) was gradually added into the flask and stirred toform dark-red colored slurry of resin. The slurry was stirred at 90° C.overnight. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated beads were dried under air to a final moisturecontent of 47% g H₂O/g wet resin. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 4.36 mmol/gdry resin.

Example 58 Preparation of poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-divinylbenzene)

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged 1-methylimidazole (18 mL, 223.5 mmol). Acetone (75 mL) was addedinto the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (8% DVB, Cl⁻density=4.0 mmol/g dry resin, 40.06, 153.7 mmol) was charged into flaskwhile stirring until a uniform suspension was obtained. The resultingreaction mixture was refluxed for 24h. After cooling, the reactionmixture was filtered using fritted glass funnel under vacuum, washedsequentially with acetone and ethyl acetate, and dried at 70° C.overnight. The chemical functionalization of the polymer resin withmethylimidazolium chloride groups was determined to be 3.54 mmol/g dryresin via titrimetry.

Example 59 Preparation of sulfonatedpoly(styrene-co-vinylbenzylmethylimidazoliumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene)(30.08 g) was charged into a 500 mL flask equipped with a magnetic stirbar and condenser. Fuming sulfuric acid (20% free SO₃, 120 mL) wasgradually added into the flask and stirred to form dark-red coloredslurry of resin. The slurry was stirred at 90° C. overnight. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed repeatedly with de-ionized water until theeffluent was neutral, as determined by pH paper. The sulfonated beadswere dried under air to a final moisture content of 50% g H₂O/g wetresin. The chemical functionalization of the polymer resin with sulfonicacid groups was determined to be 2.87 mmol/g dry resin.

Example 60 Preparation of poly(styrene-co-vinylbenzylmethylimidazoliumchloride-co-divinylbenzene)

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged 1-methylimidazole (20 mL, 248.4 mmol). Acetone (75 mL) was addedinto the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (4% DVB, Cl⁻density=5.2 mmol/g dry resin, 40.08, 203.8 mmol) was charged into flaskwhile stirring until a uniform suspension was obtained. The resultingreaction mixture was refluxed for 24h. After cooling, the reactionmixture was filtered using fritted glass funnel under vacuum, washedsequentially with acetone and ethyl acetate, and dried at 70° C.overnight. The chemical functionalization of the polymer resin withmethylimidazolium chloride groups was determined to be 3.39 mmol/g dryresin via titrimetry.

Example 61 Preparation of sulfonatedpoly(styrene-co-vinylbenzylmethylimidazoliumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene)(30.14 g) was charged into a 500 mL flask equipped with a magnetic stirbar and condenser. Fuming sulfuric acid (20% free SO₃, 120 mL) wasgradually added into the flask and stirred to form dark-red coloredslurry of resin. The slurry was stirred at 90° C. overnight. Aftercooling, the reaction mixture was filtered using fritted glass funnelunder vacuum and then washed repeatedly with de-ionized water until theeffluent was neutral, as determined by pH paper. The sulfonated beadswere dried under air to a final moisture content of 55% g H₂O/g wetresin. The chemical functionalization of the polymer resin with sulfonicacid groups was determined to be 2.78 mmol/g dry resin.

Example 62 Preparation ofpoly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene)

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged triphenylphosphine (44.32 g, 163.9 mmol). Acetone (50 mL) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (13% DVBmacroporous resin, Cl⁻ density=4.14 mmol/g dry resin, 30.12 g, 115.6mmol) was charged into flask while stirring until a uniform suspensionwas obtained. The resulting reaction mixture was refluxed for 24 h.After cooling, the reaction mixture was filtered using fritted glassfunnel under vacuum, washed sequentially with acetone and ethyl acetate,and dried at 70° C. overnight.

Example 63 Preparation of sulfonatedpoly(styrene-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene) (30.22 g) was charged into a 500 mL flaskequipped with a magnetic stir bar and condenser. Fuming sulfuric acid(20% free SO₃, 90 mL) was gradually added into the flask and stirred toform dark-red colored slurry of resin. The slurry was stirred at 90° C.for 1 hour. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated beads were dried under air to a final moisturecontent of 46% g H₂O/g wet resin. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 2.82 mmol/gdry resin.

Example 64 Preparation ofpoly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene)

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged triphenylphosphine (55.02 g, 207.7 mmol). Acetone (50 mL) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (6.5% DVBmacroporous resin, Cl⁻ density=5.30 mmol/g dry resin, 30.12 g, 157.4mmol) was charged into flask while stiffing until a uniform suspensionwas obtained. The resulting reaction mixture was refluxed for 24 h.After cooling, the reaction mixture was filtered using fritted glassfunnel under vacuum, washed sequentially with acetone and ethyl acetate,and dried at 70° C. overnight.

Example 65 Preparation of sulfonatedpoly(styrene-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene) (30.12 g) was charged into a 500 mL flaskequipped with a magnetic stir bar and condenser. Fuming sulfuric acid(20% free SO₃, 90 mL) was gradually added into the flask and stirred toform dark-red colored slurry of resin. The slurry was stirred at 90° C.for 1 hour. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated beads were dried under air to a final moisturecontent of 49% g H₂O/g wet resin. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 2.82 mmol/gdry resin.

Example 66 Preparation ofpoly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene)

To a 250 mL flask equipped with a magnetic stir bar and condenser wascharged triphenylphosphine (38.42 g, 145.0 mmol). Acetone (50 mL) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (4% DVB, Cl⁻density=4.10 mmol/g dry resin, 30.12 g, 115.4 mmol) was charged intoflask while stirring until a uniform suspension was obtained. Theresulting reaction mixture was refluxed for 24 h. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with acetone and ethyl acetate, and dried at 70° C.overnight.

Example 67 Preparation of sulfonatedpoly(styrene-co-vinylbenzyltriphenylphosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene) (30.18 g) was charged into a 500 mL flaskequipped with a magnetic stir bar and condenser. Fuming sulfuric acid(20% free SO₃, 120 mL) was gradually added into the flask and stirred toform dark-red colored slurry of resin. The slurry was stirred at 90° C.overnight. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated beads were dried under air to a final moisturecontent of 59% g H₂O/g wet resin. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 3.03 mmol/gdry resin.

Example 68 Preparation ofpoly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene)

To a 500 mL flask equipped with a magnetic stir bar and condenser wascharged triphenylphosphine (44.22 g, 166.9 mmol). Acetone (70 mL) wasadded into the flask and mixture was stirred at 50° C. for 10 min.Poly(styrene-co-vinylbenzylchloride-co-divinylbenzene) (4% DVB, Cl⁻density=3.9 mmol/g dry resin, 35.08 g, 130.4 mmol) was charged intoflask while stirring until a uniform suspension was obtained. Theresulting reaction mixture was refluxed for 24 h. After cooling, thereaction mixture was filtered using fritted glass funnel under vacuum,washed sequentially with acetone and ethyl acetate, and dried at 70° C.overnight.

Example 69 Preparation of sulfonatedpoly(styrene-co-vinylbenzyltriphenyl phosphoniumbisulfate-co-divinylbenzene)

Poly(styrene-co-vinylbenzyltriphenylphosphoniumchloride-co-divinylbenzene) (30.42 g) was charged into a 500 mL flaskequipped with a magnetic stir bar and condenser. Fuming sulfuric acid(20% free SO₃, 120 mL) was gradually added into the flask and stirred toform dark-red colored slurry of resin. The slurry was stirred at 90° C.overnight. After cooling, the reaction mixture was filtered usingfritted glass funnel under vacuum and then washed repeatedly withde-ionized water until the effluent was neutral, as determined by pHpaper. The sulfonated beads were dried under air to a final moisturecontent of 57% g H₂O/g wet resin. The chemical functionalization of thepolymer resin with sulfonic acid groups was determined to be 3.04 mmol/gdry resin.

Example 70 Preparation of poly(butyl-vinylimidazoliumchloride-co-butylimidazolium chloride-co-styrene)

To a 500 mL flask equipped with a mechanical stirrer and refluxcondenser is added 250 mL of acetone, 10 g of imidazole, 14g ofvinylimidazole, 15g of styrene, 30 g of dichlorobutane and 1 g ofazobisisobutyronitrile (AIBN). The solution is stirred under refluxconditions for 12 hours to produce a solid mass of polymer. The solidpolymer is removed from the flask, washed repeatedly with acetone, andground to a coarse powder using a mortar and pestle to yield theproduct.

Example 71 Preparation of sulfonated poly(butyl-vinylimidazoliumbisulfate-co-butylimidazolium bisulfate-co-styrene)

Poly(butyl-vinylimidazolium chloride-co-butylimidazoliumchloride-co-styrene) 30.42 g) is charged into a 500 mL flask equippedwith a mechanical stirrer. Fuming sulfuric acid (20% free SO₃, 120 mL)is gradually added into the flask until the polymer is fully suspended.The resulting slurry is stirred at 90° C. for 5 hours. After cooling,the reaction mixture is filtered using fritted glass funnel under vacuumand then washed repeatedly with de-ionized water until the effluent isneutral, as determined by pH paper.

Catalytic Digestion of Lignocellulosic Materials Example B1 Digestion ofSugarcane Bagasse using Catalyst described in Example 3

Sugarcane bagasse (50% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. The compositionof the lignocellulosic biomass was determined using a method based onthe procedures known in the art. See R. Ruiz and T. Ehrman,“Determination of Carbohydrates in Biomass by High Performance LiquidChromatography,” NREL Laboratory Analytical Procedure LAP-002 (1996); D.Tempelton and T. Ehrman, “Determination of Acid-Insoluble Lignin inBiomass,” NREL Laboratory Analytical Procedure LAP-003 (1995); T.Erhman, “Determination of Acid-Soluble Lignin in Biomass,” NRELLaboratory Analytical Procedure LAP-004 (1996); and T. Ehrman, “StandardMethod for Ash in Biomass,” NREL Laboratory Analytical Procedure LAP-005(1994).

To a 15 mL cylindrical glass reaction vial was added: 0.50 g of the canebagasse sample, 0.30 g of Catalyst as prepared in Example 3 (initialmoisture content: 12% g H₂O/g dispensed catalyst), and 800 μL ofdeionized H₂O. The reactants were mixed thoroughly with a glass stir rodto distribute the catalyst particles evenly throughout the biomass. Theresulting mixture was gently compacted to yield a solid reactant cake.The glass reactor was sealed with a phenolic cap and incubated at 120°C. for four hours.

Example B2 Separation of Catalyst/Product Mixture from the Hydrolysis ofSugarcane Bagasse

The cylindrical glass reactor from Example 41 was cooled to roomtemperature and unsealed. 5.0 mL of distilled H₂O was added to the vialreactor and the resulting mixture of liquids and solids was agitated for2 minutes by magnetic stirring. Following agitation, the solids wereallowed to sediment for 30 seconds to produce the layered mixture. Thesolid catalyst formed a layer at the bottom of the vial reactor. Ligninand residual biomass formed a solid layer above the solid catalyst. Theshort-chained beta-glucans formed a layer of amorphous solids above thelignin and residual biomass. Finally, the soluble sugars formed a liquidlayer above the short-chained beta-glucans.

Example B3 Recovery of Sugars and Soluble Carbohydrates from theHydrolysis of Sugarcane Bagasse

The supernatant and residual insoluble materials from Example 42 wereseparated by decantation. The soluble-sugar content of hydrolysisproducts was determined by a combination of high performance liquidchromatography (HPLC) and spectrophotometric methods. HPLC determinationof soluble sugars and oligosaccharides was performed on aHewlett-Packard 1050 Series instrument equipped with a refractive index(RI) detector using a 30 cm×7.8 mm Phenomenex HPB column with water asthe mobile phase. The sugar column was protected by both alead-exchanged sulfonated-polystyrene guard column and atri-alkylammoniumhydroxide anionic-exchange guard column. All HPLCsamples were microfiltered using a 0.2 μm syringe filter prior toinjection. Sample concentrations were determined by reference to acalibration generated from known standards.

The ability of the catalyst to hydrolyze the cellulose and hemicellulosecomponents of the biomass to soluble sugars was measured by determiningthe effective first-order rate constant. The extent of reaction for achemical species (e.g., glucan, xylan, arabinan) was determined bycalculating the ratio of moles of the recovered species to thetheoretical moles of the species that would be obtained as a result ofcomplete conversion of the input reactant based on the known compositionof the input biomass and the known molecular weights of the reactantsand products and the known stoichiometries of the reactions underconsideration.

For the digestion of sugarcane bagasse using catalyst as described inExample 3, the first-order rate constant for conversion of xylan toxylose was determined to be 0.3/hr. The first-order rate constant forconversion of glucan to soluble monosaccharides and oligosaccharides(including disaccharides) was determined to be 0.08/hr.

Example B4 Recovery of Insoluble Oligo-Glucans from Hydrolyzed SugarcaneBagasse

An additional 5.0 mL of water was added to the residual solids fromExample 43 and the mixture was gently agitated to suspend only thelightest particles. The suspension was decanted to remove the lightparticles from the residual lignin and residual catalyst, which remainedin the solid sediment at the bottom of the reactor. The solid particleswere concentrated by centrifugation.

The number average degree of polymerization (DOP_(N)) of residualwater-insoluble glucans (including short-chain oligosaccharides) wasdetermined by extracting the glucans into ice-cold phosphoric acid,precipitating the extracted carbohydrates into water, and measuring theratio of terminal reducing sugars to the number of total sugar monomersthe method of Zhang and Lynd. See Y.-H. Percival Zhang and Lee R. Lynd,“Determination of the Number-Average Degree of Polymerization ofCellodextrins and Cellulose with Application to Enzymatic Hydrolysis,”Biomacromolecules, 6, 1510-1515 (2005). UV-Visible spectrophotometricanalysis was performed on a Beckman DU-640 instrument. In cases wherethe digestion of hemicellulose was complete (as determined by HPLC), DOPdetermination of the residual cellulose was performed without the needfor phosphoric acid extraction. In some cases, the number average degreeof polymerization was verified by Gel Permeation Chromatography (GPC)analysis of cellulose was performed using a procedure adapted from themethod of Evans et al. See R. Evans, R. Wearne, A. F. A. Wallis,“Molecular Weight Distribution of Cellulose as Its Tricarbanilate byHigh Performance Size Exclusion Chromatography,” J. Appl. Pol. Sci., 37,3291-3303 (1989).

In a 20 mL reaction vial containing 3 mL of dry DMSO, was suspended anapproximately 50 mg sample of cellulose (dried overnight at 50° C. underreduced pressure). The reaction vial was sealed with a PFTE septum,flushed with dry N₂, followed by addition of 1.0 mL phenylisocyanate viasyringe. The reaction mixture was incubated at 60° C. for 4 hours withperiodic mixing, until the majority of cellulose was dissolved. Excessisocyanate was quenched by addition of 1.0 mL of dry MeOH. Residualsolids were pelletized by centrifugation, and a 1 mL aliquot of thesupernatant was added to 5 mL of 30% v/v MeOH/dH₂O to yield thecarbanilated cellulose as an off-white precipitate. The product wasrecovered by centrifugation, and repeatedly washed with 30% v/v MeOH,followed by drying for 10 hours at 50° C. under reduced pressure. GPCwas performed on a Hewlett-Packard 1050 Series HPLC using a series ofTSK-Gel (G3000 Hhr, G4000 Hhr, G5000 Hhr) columns and tetrahydrofuran(THF) as the mobile phase with UV/Vis detection. The molecular weightdistribution of the cellulose was determined using a calibration basedon polystyrene standards of known molecular weight.

For the digestion of sugarcane bagasse using catalyst as shown inExample 3, the number average degree of polymerization of theoligo-glucans was determined to be 19±4 anhydroglucose (AHG) units. Theobserved reduction of the degree of polymerization of the residualcellulose to a value significantly lower than the degree ofpolymerization for the crystalline domains of the input cellulose (forwhich DOP_(N)>200 AHG units) indicates that the catalyst successfullyhydrolyzed crystalline cellulose. The first order rate constant forconversion of β-glucan to short-chain oligo-glucans was determined to be0.2/hr.

Example B5 Separation and Recovery of Lignin, Residual Unreacted Biomassand Catalyst from Hydrolyzed Sugarcane Bagasse

An additional 10 mL of water was added to the residual solids in Example44. The mixture was agitated to suspend the residual lignin (andresidual unreacted biomass particles) without suspending the catalyst.The recovered catalyst was washed with water and then dried to constantmass at 110° C. in a gravity oven to yield 99.6% g/g recovery. Thefunctional density of sulfonic acid groups on the recovered catalyst wasdetermined to be 1.59±0.02 mmol/g by titration of the recovered catalystindicating negligible loss of acid functionalization.

Example B6 Reuse of Recovered Catalyst

Some of the catalyst recovered from Example 45 (0.250 g dry basis) wasreturned to the 15 mL cylindrical vial reactor. 0.50 g of additionalbiomass (composition identical to that in Example 45) and 800 μL ofdeionized H₂O was added to the reactor, and the contents were mixedthoroughly, as described in Example 41. The reactor was sealed andincubated at 115° C. for four hours. Following the reaction, the productmixture was separated following the procedure described in Examples42-45. The first-order rate constant for conversion of xylan to xylosewas determined to be 0.3/hr. The first-order rate constant forconversion of glucan to soluble monosaccharides and oligosaccharides(including disaccharides) was determined to be 0.1/hr. The numberaverage degree of polymerization of residual cellulose was determined tobe DOP_(N)=20±4 AHG units, and the first order rate constant forconversion of β-glucan to short-chain oligo-glucans was determined to be0.2/hr.

Example B7 Hydrolysis of Corn Stover Using Catalyst as Prepared inExample 34

Corn stover (7.2% g H₂O/g wet biomass, with a dry-matter composition of:33.9% g glucan/g dry biomass, 24.1% g xylan/g dry biomass, 4.8% garabinan/g dry biomass, 1.5% g galactan/g dry biomass, 4.0% g acetate/gdry biomass, 16.0% g soluble extractives/g dry biomass, 11.4% g lignin/gdry biomass, and 1.4% g ash/g dry biomass) was cut such that the maximumparticle size was no greater than 1 cm. To a 15 mL cylindrical glassreaction vial was added: 0.45 g of the cane bagasse sample, 0.22 g ofCatalyst as prepared in Example 34 (initial moisture content: 0.8% gH₂O/g dispensed catalyst), and 2.3 mL of deionized H₂O. The reactantswere mixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 110° C. for five hours.Following the reaction, the product mixture was separated following theprocedure described in Examples 42-45. The first-order rate constant forconversion of xylan to xylose was determined to be 0.1/hr. Thefirst-order rate constant for conversion of glucan to solublemonosaccharides and oligosaccharides (including disaccharides) wasdetermined to be 0.04/hr. The number average degree of polymerization ofresidual cellulose was determined to be DOP_(N)=20±4 AHG units, and thefirst order rate constant for conversion of β-glucan to short-chainoligo-glucans was determined to be 0.06/hr.

Example B8 Hydrolysis of Oil Palm Empty Fruit Bunches Using Catalyst asPrepared in Example 20

Shredded oil palm empty fruit bunches (8.7% g H₂O/g wet biomass, with adry-matter composition of: 35.0% g glucan/g dry biomass, 21.8% g xylan/gdry biomass, 1.8% g arabinan/g dry biomass, 4.8% g acetate/g drybiomass, 9.4% g soluble extractives/g dry biomass, 24.2% g lignin/g drybiomass, and 1.2% g ash/g dry biomass) was cut such that the maximumparticle size was no greater than 1 cm. To a 15 mL cylindrical glassreaction vial was added: 0.46 g of the cane bagasse sample, 0.43 g ofCatalyst as prepared in Example 20 (initial moisture content: 18.3% gH₂O/g dispensed catalyst), and 1.3 mL of deionized H₂O. The reactantswere mixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 110° C. for five hours.Following the reaction, the product mixture was separated following theprocedure described in Examples 42-45. The first-order rate constant forconversion of xylan to xylose was determined to be 0.4/hr. Thefirst-order rate constant for conversion of glucan to solublemonosaccharides and oligosaccharides (including disaccharides) wasdetermined to be 0.04/hr. The number average degree of polymerization ofresidual cellulose was determined to be DOP_(N)=20±4 AHG units, and thefirst order rate constant for conversion of β-glucan to short-chainoligo-glucans was determined to be 0.06/hr.

Example B9 Hydrolysis of Sugarcane Bagasse Using Catalyst as prepared inExample 32

Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 0.53 g of the cane bagassesample, 0.52 g of Catalyst as prepared in Example 32 (initial moisturecontent: 3.29% g H₂O/g dispensed catalyst), and 1.4 mL of deionized H₂O.The reactants were mixed thoroughly with a glass stir rod to distributethe catalyst particles evenly throughout the biomass. The resultingmixture was gently compacted to yield a solid reactant cake. The glassreactor was sealed with a phenolic cap and incubated at 115° C. for fourhours. Following the reaction, the product mixture was separatedfollowing the procedure described in Examples 42-45. The first-orderrate constant for conversion of xylan to xylose was determined to be0.59/hr. The first-order rate constant for conversion of glucan tosoluble monosaccharides and oligosaccharides (including disaccharides)was determined to be 0.05/hr. The number average degree ofpolymerization of residual cellulose was determined to be DOP_(N)=23±4AHG units, and the first order rate constant for conversion of β-glucanto short-chain oligo-glucans was determined to be 0.07/hr.

Example B10 Hydrolysis of Sugarcane Bagasse Using Catalyst as Preparedin Example 18

Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 0.51 g of the cane bagassesample, 0.51 g of Catalyst as prepared in Example 18 (initial moisturecontent: 7.9% g H₂O/g dispensed catalyst), and 1.4 mL of deionized H₂O.The reactants were mixed thoroughly with a glass stir rod to distributethe catalyst particles evenly throughout the biomass. The resultingmixture was gently compacted to yield a solid reactant cake. The glassreactor was sealed with a phenolic cap and incubated at 115° C. for fourhours. Following the reaction, the product mixture was separatedfollowing the procedure described in Examples 42-45. The first-orderrate constant for conversion of xylan to xylose was determined to be0.06/hr. The first-order rate constant for conversion of glucan tosoluble oligo-, di-, and mono-saccharides was determined to be 0.05/hr.The number average degree of polymerization of residual cellulose wasdetermined to be 20±4 AHG units, and the first order rate constant forconversion of β-glucan to short-chain oligo-glucans was determined to be0.07/hr.

Example B11 High-Selectivity to Sugars

Shredded oil palm empty fruit bunches (8.7% g H₂O/g wet biomass, with adry-matter composition of: 35.0% g glucan/g dry biomass, 21.8% g xylan/gdry biomass, 1.8% g arabinan/g dry biomass, 4.8% g acetate/g drybiomass, 9.4% g soluble extractives/g dry biomass, 24.2% g lignin/g drybiomass, and 1.2% g ash/g dry biomass) was cut such that the maximumparticle size was no greater than 1 cm. To a 15 mL cylindrical glassreaction vial was added: 0.51 g of the cane bagasse sample, 0.51 g ofCatalyst as prepared in Example 3 (initial moisture content: 8.9% gH₂O/g dispensed catalyst), and 2.6 mL of deionized H₂O. The reactantswere mixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 115° C. for four hours.Following the reaction, 10.0 mL of deionized H₂O was added to theproduct mixture to dissolve the soluble species and the solids wereallowed to sediment. HPLC determination of sugar dehydration productsand organic acids liberated from biomass samples was performed on anAgilent 1100 Series instrument using a 30 cm×7.8 mm Supelcogel™ H column(or a Phenomenex HOA column in some cases) with 0.005N sulfuric acid inwater as the mobile phase. Quantitation of sugar degradation products:formic acid, levulinic acid, 5-hydroxymethylfurfural, and 2-furaldehyde,was performed by reference to a calibration curve generated fromhigh-purity solutions of known concentration. The first order rateconstant for the production of degradation products was found to be<0.001/hr, representing >99% mol sugars/mol degradation products.

Example B12 Fermentation of Cellulosic Sugars from Sugarcane Bagasse

Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 1.6 g of the cane bagassesample, 1.8 g of Catalyst as prepared in Example 3 (initial moisturecontent: 12.1% g H₂O/g dispensed catalyst), and 5.0 mL of deionized H₂O.The reactants were mixed thoroughly with a glass stir rod to distributethe catalyst particles evenly throughout the biomass. The resultingmixture was gently compacted to yield a solid reactant cake. The glassreactor was sealed with a phenolic cap and incubated at 110° C. for fivehours. After five hours, an additional 1.0 mL of distilled H2O was addedto the reaction mixture, which was then incubated at 105° C. for anadditional 2 hours. The wet reactant cake was loaded into a syringeequipped with a 0.2 micrometer filter and the hydrolysate was pressedout of the product mixture into a sterile container. To a culture tubewas added 2.5 mL of culture media (prepared by diluting 10 g of yeastextract and 20 g peptone to 500 mL in distilled water, followed bypurification by sterile filtration), 2.5 mL of the hydrolysate, and 100mL of yeast slurry (prepared by dissolving 500 mg of Alcotec 24 hourTurbo Super yeast into 5 mL of 30° C. of sterile H₂O. The culture wasgrown at 30° C. in shaking incubator, with 1 mL aliquots removed at 24,48 and 72 hours. For each aliquot, the optical density of the culturewas determined by spectrophotometer aliquot. The aliquot was purified bycentrifugation and the supernatant was analyzed by HPLC to determine theconcentrations of glucose, xylose, galactose, arabinose, ethanol, andglycerol. After 24 hours, ethanol and glycerol were found in thefermentation supernatant, indicating at least 65% fermentation yield ona molar basis relative to the initial glucose in the hydrolysate.

Example B13 Fermentation of Cellulosic Sugars from Cassava Stem

Cassava stem (2.0% g H₂O/g wet cassava stem, with a dry-mattercomposition of: 53.0% g glucan/g dry biomass, 6.0% g xylan/g drybiomass, 2.5% g arabinan/g dry biomass, 5.5% g acetate/g dry biomass,5.9% g soluble extractives/g dry biomass, 24.2% g lignin/g dry biomass,and 2.1% g ash/g dry biomass) was shredded in a coffee-grinder such thatthe maximum particle size was no greater than 2 mm. To a 15 mLcylindrical glass reaction vial was added: 1.9 g of the shredded cassavastem, 2.0 g of Catalyst as prepared in Example 3 (initial moisturecontent: 12.0% g H₂O/g dispensed catalyst), and 8.0 mL of deionized H₂O.The reactants were mixed thoroughly with a glass stir rod to distributethe catalyst particles evenly throughout the biomass. The resultingmixture was gently compacted to yield a solid reactant cake. The glassreactor was sealed with a phenolic cap and incubated at 110° C. for fivehours. After five hours, an additional 2.0 mL of distilled H2O was addedto the reaction mixture, which was then incubated at 105° C. for anadditional 2 hours. The wet reactant cake was loaded into a syringeequipped with a 0.2 micrometer filter and the hydrolysate was pressedout of the product mixture into a sterile container. To a culture tubewas added 2.5 mL of culture media (prepared by diluting 10 g of yeastextract and 20 g peptone to 500 mL in distilled water, followed bypurification by sterile filtration), 2.5 mL of the hydrolysate, and 100mL of yeast slurry (prepared by dissolving 500 mg of Alcotec 24 hourTurbo Super yeast into 5 mL of 30° C. of sterile H₂O. The culture wasgrown at 30° C. in shaking incubator, with 1 mL aliquots removed at 24,48 and 72 hours. For each aliquot, the optical density of the culturewas determined by spectrophotometer aliquot. The aliquot was purified bycentrifugation and the supernatant was analyzed by HPLC to determine theconcentrations of glucose, xylose, galactose, arabinose, ethanol, andglycerol. After 24 hours, ethanol and glycerol were found in thefermentation supernatant, indicating at least 70% fermentation yield ona molar basis relative to the initial glucose in the hydrolysate.

Example B14 Fermentation of Glucose Obtained from Insoluble Starch

To 15 mL cylindrical glass reaction vial was added: 4.0 g of corn starch(3% g H₂O/g wet starch, with a dry-matter composition of: 98% g glucan/gdry biomass), 3.9 g of Catalyst as prepared in Example 3 (initialmoisture content: 12.25% g H₂O/g dispensed catalyst), and 12.0 mL ofdeionized H₂O. The reactants were mixed thoroughly with a glass stir rodto distribute the catalyst particles evenly throughout the biomass. Theresulting mixture was gently compacted to yield a solid reactant cake.The glass reactor was sealed with a phenolic cap and incubated at 110°C. for five hours. After five hours, an additional 2.0 mL of distilledH2O was added to the reaction mixture, which was then incubated at 105°C. for an additional 2 hours. The wet reactant cake was loaded into asyringe equipped with a 0.2 micrometer filter and the hydrolysate waspressed out of the product mixture into a sterile container. To aculture tube was added 2.5 mL of culture media (prepared by diluting 10g of yeast extract and 20 g peptone to 500 mL in distilled water,followed by purification by sterile filtration), 2.5 mL of thehydrolysate, and 100 mL of yeast slurry (prepared by dissolving 500 mgof Alcotec 24 hour Turbo Super yeast into 5 mL of 30° C. of sterile H₂O.The culture was grown at 30° C. in shaking incubator, with 1 mL aliquotsremoved at 24, 48 and 72 hours. For each aliquot, the optical density ofthe culture was determined by spectrophotometer aliquot. The aliquot waspurified by centrifugation and the supernatant was analyzed by HPLC todetermine the concentrations of glucose, xylose, galactose, arabinose,ethanol, and glycerol. After 24 hours, ethanol and glycerol were foundin the fermentation supernatant, indicating at least 88% fermentationyield on a molar basis relative to the initial glucose in thehydrolysate.

Example B15 Enzymatic Saccharification of Oligo-glucans Obtained fromDigestion of Sugarcane Bagasse with Catalyst as Prepared in Example 3

50.0 mg of the oligo-glucans obtained in Example 44 was suspended in 0.4mL of 0.05 molar acetate buffer solution at pH 4.8 in a culture tube.The suspension was pre-warmed to 40° C., after which, 0.5 FPU ofCelluclast® cellulase enzyme from Trichoderma reesei and 2 IU ofcellobiase enzyme from Aspergillus niger (diluted in 0.1 mL of citratebuffer at 40° C.) was added. A 50.0 mL aliquot was sampled from theenzymatic reaction every hour for five hours. For each aliquot, thereaction was terminated by diluting the 50.0 mL sample to 0.7 mL indistilled water and adding 0.3 mL of DNS reagent (prepared by diluting91 g of potassium sodium tartrate, 3.15 g dinitrosalicylic acid, 131 mLof 2 molar sodium hydroxide 2.5 g phenol and 2.5 g sodium sulfite to 500mL with distilled H₂O). The 1 mL mixture was sealed in a microcentrifugetube and boiled for exactly 5 minutes in water. The appearance ofreducing sugars was measured by comparing the absorbance at 540 nm to acalibration curve generated from glucose samples of known concentration.The first order rate constant for reducing sugar liberation in thesaccharification reaction was determined to be 0.15/hr.

Comparative Example B16 Attempted Hydrolysis of Sugarcane Bagasse withCross-Linked, Sulfonated-Polystyrene (Negative Control 1)

The cellulose digestion capability of the catalysts described herein wascompared to that of conventional acidified polymer-resins used forcatalysis in organic and industrial chemistry (T. Okuhara,“Water-Tolerant Solid Acid Catalysts,” Chem. Rev., 102, 3641-3666(2002)). Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 0.51 g of the cane bagassesample, 0.53 g of sulfonated polystyrene (Dowex® 50WX2 resin, acidfunctionalization: 4.8 mmol/g, initial moisture content: 19.6% g H₂O/gdispensed catalyst), and 1.4 mL of deionized H₂O. The reactants weremixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 115° C. for six hours.Following the reaction, the product mixture was separated following theprocedure described in Examples 42-45. The first-order rate constant forconversion of xylan to xylose was determined to be 0.1/hr. Thefirst-order rate constant for conversion of glucan to soluble oligo-,di-, and mono-saccharides was determined to be <0.01/hr. The numberaverage degree of polymerization of residual cellulose was found to beDOP_(N)>300 AHG units, indicating little or no digestion of crystallinecellulose in the biomass sample. Short-chain oligosaccharides were notdetected. Unlike the digestion products depicted in FIG. 1), theresidual biomass exhibited little or no structural reduction in particlesize.

Comparative Example B17 Attempted Hydrolysis of Sugarcane Bagasse withSulfonated Polystyrene (Negative Control 2)

Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 0.52 g of the cane bagassesample, 0.55 g of sulfonated polystyrene (Amberlyst® 15, acidfunctionalization: 4.6 mmol/g, initial moisture content: 10.8% g H₂O/gdispensed catalyst), and 1.8 mL of deionized H₂O. The reactants weremixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 115° C. for six hours.Following the reaction, the product mixture was separated following theprocedure described in Examples 42-45. The first-order rate constant forconversion of xylan to xylose was determined to be 0.1/hr. Thefirst-order rate constant for conversion of glucan to soluble oligo-,di-, and mono-saccharides was determined to be <0.01/hr. The numberaverage degree of polymerization of residual cellulose was determined tobe DOP_(N)>300 AHG units, indicating little or no digestion ofcrystalline cellulose in the biomass sample. Short-chainoligosaccharides were not detected. Unlike the digestion productsdepicted in FIG. 1), the residual biomass exhibited little or nostructural reduction in particle size.

Comparative Example B18 Attempted Hydrolysis of Sugarcane Bagasse withCross-Linked Polyacrylic Acid (Negative Control 3)

Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 0.50 g of the cane bagassesample, 0.50 g of polyacrylic acid beads (Amberlite® IRC86 resin, acidfunctionalization: 10.7 mmol/g, initial moisture content: 5.2% g H₂O/gdispensed catalyst), and 1.8 mL of deionized H₂O. The reactants weremixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 115° C. for six hours.Following the reaction, the product mixture was separated following theprocedure described in Examples 42-45. The first-order rate constant forconversion of xylan to xylose was determined to be <0.05/hr. Thefirst-order rate constant for conversion of glucan to soluble oligo-,di-, and mono-saccharides was determined to be <0.001/hr. The numberaverage degree of polymerization of residual cellulose was determined tobe DOP_(N)>300 AHG units, indicating little or no digestion ofcrystalline cellulose in the biomass sample. Short-chainoligosaccharides were not detected. Unlike the digestion productsdepicted in FIG. 1), the residual biomass exhibited little or nostructural reduction in particle size.

Comparative Example B19 Attempted Hydrolysis of Sugarcane Bagasse with aNon-Acidic Ionomer as Prepared in Example 2 (Negative Control 4)

Sugarcane bagasse (12.5% g H₂O/g wet bagasse, with a dry-mattercomposition of: 39.0% g glucan/g dry biomass, 17.3% g xylan/g drybiomass, 5.0% g arabinan/g dry biomass, 1.1% g galactan/g dry biomass,5.5% g acetate/g dry biomass, 5.0% g soluble extractives/g dry biomass,24.1% g lignin/g dry biomass, and 3.1% g ash/g dry biomass) was cut suchthat the maximum particle size was no greater than 1 cm. To a 15 mLcylindrical glass reaction vial was added: 0.50 g of the cane bagassesample, 0.50 g ofpoly[styrene-co-3-methyl-1-(4-vinyl-benzyl)-3H-imidazol-1-iumchloride-co-divinylbenzene] (Catalyst as described in Example 2, Acidfunctionalization: 0.0 mmol/g, initial moisture content: 4.0% g H₂O/gdispensed polymer), and 1.8 mL of deionized H₂O. The reactants weremixed thoroughly with a glass stir rod to distribute the catalystparticles evenly throughout the biomass. The resulting mixture wasgently compacted to yield a solid reactant cake. The glass reactor wassealed with a phenolic cap and incubated at 115° C. for six hours.Following the reaction, the product mixture was separated following theprocedure described in Examples 42-45. The first-order rate constant forconversion of xylan to xylose was determined to be <0.001/hr. Nodetectable amounts of soluble oligo-, di-, and mono-saccharides wereobserved. It was determined that the number average degree ofpolymerization of the residual cellulose was DOP_(N)>300 AHG units,indicating little or no digestion of crystalline cellulose in thebiomass sample. Short-chain oligosaccharides were not detected. Unlikethe digestion products depicted in FIG. 1), the residual biomassappeared physically unchanged from the input form.

1. A composition comprising: biomass; and a polymer; wherein the polymercomprises acidic monomers and ionic monomers connected to form apolymeric backbone, wherein each acidic monomer comprises at least oneBronsted-Lowry acid, and wherein each ionic monomer independentlycomprises at least one nitrogen-containing cationic group or at leastone phosphorous-containing cationic group.
 2. The composition of claim1, further comprising a solvent.
 3. The composition of claim 2, whereinthe solvent comprises water.
 4. The composition of claim 1, wherein thebiomass comprises cellulose, hemicellulose, or a combination thereof. 5.The composition of claim 4, wherein the polymer is hydrogen-bonded tothe biomass to form a saccharification intermediate.
 6. The compositionof claim 1, wherein the biomass comprises chemically-hydrolyzed biomass.7. The composition of claim 6, further comprising one or more sugarsselected from monosaccharides, oligosaccharides, and a mixture thereof.8. The composition of claim 7, wherein the one or more sugars are two ormore sugars, wherein at least one of the two more sugars is a C4-C6monosaccharide, and at least one of the two or more sugars is anoligosaccharide.
 9. The composition of claim 7, wherein the one or moresugars are selected from glucose, galactose, fructose, xylose, andarabinose.
 10. The composition of claim 1, comprising no more than 5%weight/volume of the polymer.
 11. The composition of claim 1, whereinthe Bronsted-Lowry acid at each occurrence in the polymer isindependently selected from sulfonic acid, phosphonic acid, acetic acid,isophthalic acid, boronic acid, and perfluorinated acid.
 12. Thecomposition of claim 1, wherein one or more of the acidic monomers inthe polymer each further comprise a linker connecting the Bronsted-Lowryacid to the polymeric backbone, wherein the linker at each occurrence isindependently selected from unsubstituted or substituted alkylene,unsubstituted or substituted cycloalkylene, unsubstituted or substitutedalkenylene, unsubstituted or substituted arylene, unsubstituted orsubstituted heteroarylene, unsubstituted or substituted alkylene ether,unsubstituted or substituted alkylene ester, and unsubstituted orsubstituted alkylene carbamate.
 13. The composition of claim 1, whereinthe nitrogen-containing cationic group in the polymer at each occurrenceis independently selected from pyrrolium, imidazolium, pyrazolium,oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium,pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, andpyrollizinium.
 14. The composition of claim 1, wherein thephosphorous-containing cationic group in the polymer at each occurrenceis independently selected from triphenyl phosphonium, trimethylphosphonium, triethyl phosphonium, tripropyl phosphonium, tributylphosphonium, trichloro phosphonium, and trifluoro phosphonium.
 15. Thecomposition of claim 1, wherein one or more of the ionic monomers in thepolymer each further comprise a linker connecting thenitrogen-containing cationic group or the phosphorous-containingcationic group to the polymeric backbone, wherein the linker at eachoccurrence is independently selected from unsubstituted or substitutedalkylene, unsubstituted or substituted cycloalkylene, unsubstituted orsubstituted alkenylene, unsubstituted or substituted arylene,unsubstituted or substituted heteroarylene, unsubstituted or substitutedalkylene ether, unsubstituted or substituted alkylene ester, andunsubstituted or substituted alkylene carbamate.
 16. The composition ofclaim 1, wherein the polymeric backbone in the polymer is selected frompolyethylene, polypropylene, polyvinyl alcohol, polystyrene,polyurethane, polyvinyl chloride, polyphenol-aldehyde,polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam,poly(acrylonitrile butadiene styrene), polyalkyleneammonium,polyalkylenediammonium, polyalkylenepyrrolium, polyalkyleneimidazolium,polyalkylenepyrazolium, polyalkyleneoxazolium, polyalkylenethiazolium,polyalkylenepyridinium, polyalkylenepyrimidinium,polyalkylenepyrazinium, polyalkylenepyradizimium,polyalkylenethiazinium, polyalkylenemorpholinium,polyalkylenepiperidinium, polyalkylenepiperizinium,polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,polyalkylenetrimethylphosphonium, polyalkylenetriethylphosphonium,polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium,polyalkylenetrichlorophosphonium, polyalkylenetrifluorophosphonium, andpolyalkylenediazolium.
 17. The composition of claim 1, wherein thepolymer further comprises hydrophobic monomers connected to form thepolymeric backbone, wherein each hydrophobic monomer comprises ahydrophobic group, wherein the hydrophobic group at each occurrence isindependently selected from an unsubstituted or substituted alkyl, anunsubstituted or substituted cycloalkyl, an unsubstituted or substitutedaryl, or an unsubstituted or substituted heteroaryl.
 18. A compositioncomprising a polymer hydrogen-bonded to biomass, wherein the polymercomprises acidic monomers and ionic monomers connected to form apolymeric backbone, wherein each acidic monomer comprises at least oneBronsted-Lowry acid, and wherein each ionic monomer independentlycomprises at least one nitrogen-containing cationic group or at leastone phosphorous-containing cationic group; and wherein the biomasscomprises cellulose, hemicellulose or a combination thereof.
 19. Thecomposition of claim 7, wherein the polymer, the one or more sugars, andthe chemically-hydrolyzed biomass are distinct components.
 20. Acomposition comprising the chemically-hydrolyzed biomass of claim 7,substantially separated from the polymer and the one or more sugars. 21.A composition comprising the polymer of claim 7, substantially separatedfrom the chemically-hydrolyzed biomass and the one or more sugars.
 22. Acomposition comprising the one or more sugars of claim 7, substantiallyseparated from the chemically-hydrolyzed biomass and the polymer.